Pesticidal compositions and processes related thereto

ABSTRACT

This document discloses pesticidal compostions comprising molecules having the following formulas: 
                         
and processes related thereto.

CROSS-REFERENCE TO RELATED APPLICATIONS

This Application is a continuation of U.S. patent application Ser. No.13/368,384, which was filed on Feb. 8, 2012, and which claims priorityfrom, and benefit of, U.S. provisional application 61/440,910, which wasfiled on Feb. 9, 2011, the entire content of these applications arehereby incorporated by reference into this Application.

FIELD OF THE INVENTION

The invention disclosed in this document is related to the field ofprocesses to produce molecules that are useful as pesticides (e.g.,acaricides, insecticides, molluscicides, and nematicides), suchmolecules, and processes of using such molecules to control pests.

BACKGROUND OF THE INVENTION

Pests cause millions of human deaths around the world each year.Furthermore, there are more than ten thousand species of pests thatcause losses in agriculture. The worldwide agricultural losses amount tobillions of U.S. dollars each year.

Termites cause damage to all kinds of private and public structures. Theworld-wide termite damage losses amount to billions of U.S. dollars eachyear.

Stored food pests eat and adulterate stored food. The world-wide storedfood losses amount to billions of U.S. dollars each year, but moreimportantly, deprive people of needed food.

There is an acute need for new pesticides. Certain pests are developingresistance to pesticides in current use. Hundreds of pest species areresistant to one or more pesticides. The development of resistance tosome of the older pesticides, such as DDT, the carbamates, and theorganophosphates, is well known. But resistance has even developed tosome of the newer pesticides.

Therefore, for many reasons, including the above reasons, a need existsfor new pesticides.

DEFINITIONS

The examples given in the definitions are generally non-exhaustive andmust not be construed as limiting the invention disclosed in thisdocument. It is understood that a substituent should comply withchemical bonding rules and steric compatibility constraints in relationto the particular molecule to which it is attached.

“Acaricide Group” is defined under the heading “ACARICIDES”.

“AI Group” is defined after the place in this document where the“Herbicide Group” is defined.

“Alkenyl” means an acyclic, unsaturated (at least one carbon-carbondouble bond), branched or unbranched, substituent consisting of carbonand hydrogen, for example, vinyl, allyl, butenyl, pentenyl, and hexenyl.

“Alkenyloxy” means an alkenyl further consisting of a carbon-oxygensingle bond, for example, allyloxy, butenyloxy, pentenyloxy, hexenyloxy.

“Alkoxy” means an alkyl further consisting of a carbon-oxygen singlebond, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy,isobutoxy, and tert-butoxy.

“Alkyl” means an acyclic, saturated, branched or unbranched, substituentconsisting of carbon and hydrogen, for example, methyl, ethyl, propyl,isopropyl, butyl, and tert-butyl.

“Alkynyl” means an acyclic, unsaturated (at least one carbon-carbontriple bond), branched or unbranched, substituent consisting of carbonand hydrogen, for example, ethynyl, propargyl, butynyl, and pentynyl.

“Alkynyloxy” means an alkynyl further consisting of a carbon-oxygensingle bond, for example, pentynyloxy, hexynyloxy, heptynyloxy, andoctynyloxy.

“Aryl” means a cyclic, aromatic substituent consisting of hydrogen andcarbon, for example, phenyl, naphthyl, and biphenyl.

“Cycloalkenyl” means a monocyclic or polycyclic, unsaturated (at leastone carbon-carbon double bond) substituent consisting of carbon andhydrogen, for example, cyclobutenyl, cyclopentenyl, cyclohexenyl,norbornenyl, bicyclo[2.2.2]octenyl, tetrahydronaphthyl,hexahydronaphthyl, and octahydronaphthyl.

“Cycloalkenyloxy” means a cycloalkenyl further consisting of acarbon-oxygen single bond, for example, cyclobutenyloxy,cyclopentenyloxy, norbornenyloxy, and bicyclo[2.2.2]octenyloxy.

“Cycloalkyl” means a monocyclic or polycyclic, saturated substituentconsisting of carbon and hydrogen, for example, cyclopropyl, cyclobutyl,cyclopentyl, norbornyl, bicyclo[2.2.2]octyl, and decahydronaphthyl.

“Cycloalkoxy” means a cycloalkyl further consisting of a carbon-oxygensingle bond, for example, cyclopropyloxy, cyclobutyloxy, cyclopentyloxy,norbornyloxy, and bicyclo[2.2.2]octyloxy.

“Fungicide Group” is defined under the heading “FUNGICIDES.”

“Halo” means fluoro, chloro, bromo, and iodo.

“Haloalkoxy” means an alkoxy further consisting of, from one to themaximum possible number of identical or different, halos, for example,fluoromethoxy, trifluoromethoxy, 2,2-difluoropropoxy, chloromethoxy,trichloromethoxy, 1,1,2,2-tetrafluoroethoxy, and pentafluoroethoxy.

“Haloalkyl” means an alkyl further consisting of, from one to themaximum possible number of, identical or different, halos, for example,fluoromethyl, trifluoromethyl, 2,2-difluoropropyl, chloromethyl,trichloromethyl, and 1,1,2,2-tetrafluoroethyl.

“Herbicide Group” is defined under the heading “HERBICIDES.”

“Heterocyclyl” means a cyclic substituent that may be fully saturated,partially unsaturated, or fully unsaturated, where the cyclic structurecontains at least one carbon and at least one heteroatom, where saidheteroatom is nitrogen, sulfur, or oxygen. Examples of aromaticheterocyclyls include, but are not limited to, benzofuranyl,benzoisothiazolyl, benzoisoxazolyl, benzoxazolyl, benzothienyl,benzothiazolyl cinnolinyl, furanyl, indazolyl, indolyl, imidazolyl,isoindolyl, isoquinolinyl, isothiazolyl, isoxazolyl, oxadiazolyl,oxazolinyl, oxazolyl, phthalazinyl, pyrazinyl, pyrazolinyl, pyrazolyl,pyridazinyl, pyridyl, pyrimidinyl, pyrrolyl, quinazolinyl, quinolinyl,quinoxalinyl, tetrazolyl, thiazolinyl, thiazolyl, thienyl, triazinyl,and triazolyl. Examples of fully saturated heterocyclyls include, butare not limited to, piperazinyl, piperidinyl, morpholinyl, pyrrolidinyl,tetrahydrofuranyl, and tetrahydropyranyl. Examples of partiallyunsaturated heterocyclyls include, but are not limited to,1,2,3,4-tetrahydro-quinolinyl, 4,5-dihydro-oxazolyl,4,5-dihydro-1H-pyrazolyl, 4,5-dihydro-isoxazolyl, and2,3-dihydro-[1,3,4]-oxadiazolyl.

“Insecticide Group” is defined under the heading “INSECTICIDES.”

“Nematicide Group” is defined under the heading “NEMATICIDES”

“Synergist Group” is defined under the heading “SYNERGISTIC MIXTURES ANDSYNERGISTS”

DETAILED DESCRIPTION OF THE INVENTION

This document discloses molecules having the following formulas:

wherein:

(a) Ar₁ is (each independently)

-   -   (1) furanyl, phenyl, pyridazinyl, pyridyl, pyrimidinyl, thienyl,        or    -   (2) substituted furanyl, substituted phenyl, substituted        pyridazinyl, substituted pyridyl, substituted pyrimidinyl, or        substituted thienyl,        -   wherein said substituted furanyl, substituted phenyl,            substituted pyridazinyl, substituted pyridyl, substituted            pyrimidinyl, and substituted thienyl, have one or more            substituents independently selected from H, F, Cl, Br, I,            CN, NO₂, C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₃-C₆ cycloalkyl,            C₃-C₆ halocycloalkyl, C₃-C₆ cycloalkoxy, C₃-C₆            halocycloalkoxy, C₁-C₆ alkoxy, C₁-C₆ haloalkoxy, C₂-C₆            alkenyl, C₂-C₆ alkynyl, S(═O)_(n)(C₁-C₆ alkyl),            S(═O)_(n)(C₁-C₆ haloalkyl), OSO₂(C₁-C₆ alkyl), OSO₂(C₁-C₆            halo alkyl), C(═O)NR_(x)R_(y), (C₁-C₆ alkyl)NR_(x)R_(y),            C(═O)(C₁-C₆ alkyl), C(═O)O(C₁-C₆ alkyl), C(═O)(C₁-C₆            haloalkyl), C(═O)O(C₁-C₆ haloalkyl), C(═O)(C₃-C₆            cycloalkyl), C(═O)O(C₃-C₆ cycloalkyl), C(═O)(C₂-C₆ alkenyl),            C(═O)O(C₂-C₆ alkenyl), (C₁-C₆ alkyl)O(C₁-C₆ alkyl), (C₁-C₆            alkyl)S(C₁-C₆ alkyl), C(═O)(C₁-C₆ alkyl)C(═O)O(C₁-C₆ alkyl),            phenyl, phenoxy, substituted phenyl, and substituted            phenoxy,        -   wherein such substituted phenyl and substituted phenoxy have            one or more substituents independently selected from H, F,            Cl, Br, I, CN, NO₂, C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₁-C₆            hydroxyalkyl, C₃-C₆ cycloalkyl, C₃-C₆ halocycloalkyl, C₃-C₆            hydroxycycloalkyl, C₃-C₆ cycloalkoxy, C₃-C₆ halocycloalkoxy,            C₃-C₆ hydroxycycloalkoxy, C₁-C₆ alkoxy, C₁-C₆ haloalkoxy,            C₂-C₆ alkenyl, C₂-C₆ alkynyl, S(═O)_(n)(C₁-C₆ alkyl),            S(═O)_(n)(C₁-C₆ haloalkyl), OSO₂(C₁-C₆ alkyl), OSO₂(C₁-C₆            haloalkyl), C(═O)NR_(x)R_(y), (C₁-C₆ alkyl)NR_(x)R_(y),            C(═O)(C₁-C₆ alkyl), C(═O)O(C₁-C₆ alkyl), C(═O)(C₁-C₆            haloalkyl), C(═O)O(C₁-C₆ haloalkyl), C(═O)(C₃-C₆            cycloalkyl), C(═O)O(C₃-C₆ cycloalkyl), C(═O)(C₂-C₆ alkenyl),            C(═O)O(C₂-C₆ alkenyl), (C₁-C₆ alkyl)O(C₁-C₆ alkyl), (C₁-C₆            alkyl)S(C₁-C₆ alkyl), C(═O)(C₁-C₆ alkyl)C(═O)O(C₁-C₆            alkyl)phenyl, and phenoxy;

(b) Het is (each independently) a 5 or 6 membered, saturated orunsaturated, heterocyclic ring, containing one or more heteroatomsindependently selected from nitrogen, sulfur, or oxygen, and where Ar₁and Ar₂ are not ortho to each other (but may be meta or para, such as,for a five membered ring they are 1,3 and for a 6 membered ring they areeither 1,3 or 1,4), and where said heterocyclic ring may also besubstituted with one or more substituents independently selected from H,OH, F, Cl, Br, I, CN, NO₂, oxo, C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₁-C₆hydroxyalkyl, C₃-C₆ cycloalkyl, C₃-C₆ halocycloalkyl, C₃-C₆hydroxycycloalkyl, C₃-C₆ cycloalkoxy, C₃-C₆ halocycloalkoxy, C₃-C₆hydroxycycloalkoxy, C₁-C₆ alkoxy, C₁-C₆ haloalkoxy, C₂-C₆ alkenyl, C₂-C₆alkynyl, S(═O)(C₁-C₆ alkyl), S(═O)_(n)(C₁-C₆ haloalkyl), OSO₂(C₁-C₆alkyl), OSO₂(C₁-C₆ haloalkyl), C(═O)NR_(x)R_(y), (C₁-C₆alkyl)NR_(x)R_(y), C(═O)(C₁-C₆ alkyl), C(═O)O(C₁-C₆ alkyl), C(═O)(C₁-C₆haloalkyl), C(═O)O(C₁-C₆ haloalkyl), C(═O)(C₃-C₆ cycloalkyl),C(═O)O(C₃-C₆ cycloalkyl), C(═O)(C₂-C₆ alkenyl), C(═O)O(C₂-C₆ alkenyl),(C₁-C₆ alkyl)O(C₁-C₆ alkyl), (C₁-C₆ alkyl)S(C₁-C₆ alkyl), C(═O)(C₁-C₆alkyl)C(═O)O(C₁-C₆ alkyl), phenyl, phenoxy, substituted phenyl andsubstituted phenoxy

-   -   wherein such substituted phenyl and substituted phenoxy have one        or more substituents independently selected from H, OH, F, Cl,        Br, I, CN, NO₂, C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₁-C₆        hydroxyalkyl, C₃-C₆ cycloalkyl, C₃-C₆ halocycloalkyl, C₃-C₆        hydroxycycloalkyl, C₃-C₆ cycloalkoxy, C₃-C₆ halocycloalkoxy,        C₃-C₆ hydroxycycloalkoxy, C₁-C₆ alkoxy, C₁-C₆ haloalkoxy, C₂-C₆        alkenyl, C₂-C₆ alkynyl, S(═O)(C₁-C₆ alkyl), S(═O)_(n)(C₁-C₆        haloalkyl), OSO₂(C₁-C₆ alkyl), OSO₂(C₁-C₆ haloalkyl), C(═O)H,        C(═O)OH, C(═O)NR_(x)R_(y), (C₁-C₆ alkyl)NR_(x)R_(y), C(═O)(C₁-C₆        alkyl), C(═O)O(C₁-C₆ alkyl), C(═O)(C₁-C₆ haloalkyl),        C(═O)O(C₁-C₆ haloalkyl), C(═O)(C₃-C₆ cycloalkyl), C(═O)O(C₃-C₆        cycloalkyl), C(═O)(C₂-C₆ alkenyl), C(═O)O(C₂-C₆ alkenyl), (C₁-C₆        alkyl)O(C₁-C₆ alkyl), (C₁-C₆ alkyl)S(C₁-C₆ alkyl), C(═O)(C₁-C₆        alkyl)C(═O)O(C₁-C₆ alkyl), phenyl, and phenoxy;

(c) Ar₂ is (each independently)

-   -   (1) furanyl, phenyl, pyridazinyl, pyridyl, pyrimidinyl, thienyl,        or    -   (2) substituted furanyl, substituted phenyl, substituted        pyridazinyl, substituted pyridyl, substituted pyrimidinyl, or        substituted thienyl,        -   wherein said substituted furanyl, substituted phenyl,            substituted pyridazinyl, substituted pyridyl, substituted            pyrimidinyl, and substituted thienyl, have one or more            substituents independently selected from H, OH, F, Cl, Br,            I, CN, NO₂, C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₁-C₆            hydroxyalkyl, C₃-C₆ cycloalkyl, C₃-C₆ halocycloalkyl, C₃-C₆            hydroxycycloalkyl, C₃-C₆ cycloalkoxy, C₃-C₆ halocycloalkoxy,            C₃-C₆ hydroxycycloalkoxy, C₁-C₆ alkoxy, C₁-C₆ haloalkoxy,            C₂-C₆ alkenyl, C₂-C₆ alkynyl, S(═O)(C₁-C₆ alkyl),            S(═O)_(n)(C₁-C₆ haloalkyl), OSO₂(C₁-C₆ alkyl), OSO₂(C₁-C₆            haloalkyl), C(═O)NR_(x)R_(y), (C₁-C₆ alkyl)NR_(x)R_(y),            C(═O)(C₁-C₆ alkyl), C(═O)O(C₁-C₆ alkyl), C(═O)(C₁-C₆            haloalkyl), C(═O)O(C₁-C₆ haloalkyl), C(═O)(C₃-C₆            cycloalkyl), C(═O)O(C₃-C₆ cycloalkyl), C(═O)(C₂-C₆ alkenyl),            C(═O)O(C₂-C₆ alkenyl), (C₁-C₆ alkyl)O(C₁-C₆ alkyl), (C₁-C₆            alkyl)S(C₁-C₆ alkyl), C(═O)(C₁-C₆ alkyl)C(═O)O(C₁-C₆ alkyl),            phenyl, phenoxy, substituted phenyl and substituted phenoxy        -   wherein such substituted phenyl and substituted phenoxy have            one or more substituents independently selected from H, OH,            F, Cl, Br, I, CN, NO₂, C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₁-C₆            hydroxyalkyl, C₃-C₆ cycloalkyl, C₃-C₆ halocycloalkyl, C₃-C₆            hydroxycycloalkyl, C₃-C₆ cycloalkoxy, C₃-C₆ halocycloalkoxy,            C₃-C₆ hydroxycycloalkoxy, C₁-C₆ alkoxy, C₁-C₆ haloalkoxy,            C₂-C₆ alkenyl, C₂-C₆ alkynyl, S(═O)(C₁-C₆ alkyl),            S(═O)_(n)(C₁-C₆ haloalkyl), OSO₂(C₁-C₆ alkyl), OSO₂(C₁-C₆            haloalkyl), C(═O)H, C(═O)OH, C(═O)NR_(x)R_(y), (C₁-C₆            alkyl)NR_(x)R_(y), C(═O)(C₁-C₆ alkyl), C(═O)O(C₁-C₆ alkyl),            C(═O)(C₁-C₆ haloalkyl), C(═O)O(C₁-C₆ haloalkyl), C(═O)(C₃-C₆            cycloalkyl), C(═O)O(C₃-C₆ cycloalkyl), C(═O)(C₁-C₆            haloalkyl), C(═O)(C₂-C₆ alkenyl), C(═O)O(C₂-C₆ alkenyl),            (C₁-C₆ alkyl)O(C₁-C₆ alkyl), (C₁-C₆ alkyl)S(C₁-C₆ alkyl),            C(═O)(C₁-C₆ alkyl)C(═O)O(C₁-C₆ alkyl), phenyl, and phenoxy);

(d) R1 and R2 are independently selected from H, C₁-C₆ alkyl, C₃-C₆cycloalkyl, C₃-C₆ hydroxycycloalkoxy, C₂-C₆ alkenyl, C₂-C₆ alkynyl,S(═O)_(n)(C₁-C₆ alkyl), OSO₂(C₁-C₆ alkyl), C(═O)H, C(═O)(C₁-C₆ alkyl),C(═O)O(C₁-C₆ alkyl), C(═O)(C₃-C₆ cycloalkyl), C(═O)O(C₃-C₆ cycloalkyl),C(═O)(C₂-C₆ alkenyl), C(═O)O(C₂-C₆ alkenyl), (C₁-C₆ alkyl)O(C₁-C₆alkyl), (C₁-C₆ alkyl)S(C₁-C₆ alkyl), C(═O)(C₁-C₆ alkyl)C(═O)O(C₁-C₆alkyl), and phenyl,

-   -   wherein each alkyl, cycloalkyl, cycloalkoxy, alkoxy, alkenyl,        alkynyl, and phenyl are optionally substituted with one or more        substituents independently selected from OH, F, Cl, Br, I, CN,        NO₂, oxo, C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₁-C₆ hydroxyalkyl,        C₃-C₆ cycloalkyl, C₃-C₆ halocycloalkyl, C₃-C₆ hydroxycycloalkyl,        C₃-C₆ cycloalkoxy, C₃-C₆ halocycloalkoxy, C₃-C₆        hydroxycycloalkoxy, C₁-C₆ alkoxy, C₁-C₆ haloalkoxy, C₂-C₆        alkenyl, C₂-C₆ alkynyl, S(═O)_(n)(C₁-C₆ alkyl), S(═O)_(n)(C₁-C₆        haloalkyl), OSO₂(C₁-C₆ alkyl), OSO₂(C₁-C₆ haloalkyl),        C(═O)NR_(x)R_(y), (C₁-C₆ alkyl)NR_(x)R_(y), C(═O)(C₁-C₆ alkyl),        C(═O)O(C₁-C₆ alkyl), C(═O)(C₁-C₆ haloalkyl), C(═O)O(C₁-C₆        haloalkyl), C(═O)(C₃-C₆ cycloalkyl), C(═O)O(C₃-C₆ cycloalkyl),        C(═O)(C₁-C₆ haloalkyl), C(═O)(C₂-C₆ alkenyl), C(═O)O(C₂-C₆        alkenyl), (C₁-C₆ alkyl)O(C₁-C₆ alkyl), (C₁-C₆ alkyl)S(C₁-C₆        alkyl), C(═O)(C₁-C₆ alkyl)C(═O)O(C₁-C₆ alkyl), phenyl, and        phenoxy)    -   optionally R1 and R2 together with the carbons to which they are        attached, form a 3-, 4-, 5-, or 6-membered carbocyclic or        heterocyclic ring that is optionally substituted with one or        more substituents independently selected from OH, F, Cl, Br, I,        CN, NO₂, oxo, C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₁-C₆ hydroxyalkyl,        C₃-C₆ cycloalkyl, C₃-C₆ halocycloalkyl, C₃-C₆ hydroxycycloalkyl,        C₃-C₆ cycloalkoxy, C₃-C₆ halocycloalkoxy, C₃-C₆        hydroxycycloalkoxy, C₁-C₆ alkoxy, C₁-C₆ haloalkoxy, C₂-C₆        alkenyl, C₂-C₆ alkynyl, S(═O)_(n)(C₁-C₆ alkyl), S(═O)_(n)(C₁-C₆        haloalkyl), OSO₂(C₁-C₆ alkyl), OSO₂(C₁-C₆ haloalkyl),        C(═O)NR_(x)R_(y), (C₁-C₆ alkyl)NR_(x)R_(y), C(═O)(C₁-C₆ alkyl),        C(═O)O(C₁-C₆ alkyl), C(═O)(C₁-C₆ haloalkyl), C(═O)O(C₁-C₆        haloalkyl), C(═O)(C₃-C₆ cycloalkyl), C(═O)O(C₃-C₆ cycloalkyl),        C(═O)(C₂-C₆ alkenyl), C(═O)O(C₂-C₆ alkenyl), (C₁-C₆        alkyl)O(C₁-C₆ alkyl), (C₁-C₆ alkyl)S(C₁-C₆ alkyl), C(═O)(C₁-C₆        alkyl)C(═O)O(C₁-C₆ alkyl), phenyl, and phenoxy;

(e) R3 is H, CN, F, Cl, Br, I, C₁-C₆ alkyl, C₃-C₆ cycloalkyl, C₃-C₆cycloalkoxy, C₁-C₆ alkoxy, C₂-C₆ alkenyl, C₂-C₆ alkynyl, S(═O)_(n)(C₁-C₆alkyl), OSO₂(C₁-C₆ alkyl), OSO₂(C₁-C₆ haloalkyl), C(═O)NR_(x)R_(y),(C₁-C₆ alkyl)NR_(x)R_(y), C(═O)(C₁-C₆ alkyl), C(═O)O(C₁-C₆ alkyl),C(═O)(C₁-C₆ haloalkyl), C(═O)O(C₁-C₆ haloalkyl), C(═O)(C₃-C₆cycloalkyl), C(═O)O(C₃-C₆ cycloalkyl), C(═O)(C₂-C₆ alkenyl),C(═O)O(C₂-C₆ alkenyl), (C₁-C₆ alkyl)O(C₁-C₆ alkyl), (C₁-C₆ alkyl)S(C₁-C₆alkyl), C(═O)(C₁-C₆ alkyl)C(═O)O(C₁-C₆ alkyl), phenyl, and phenoxy,

-   -   wherein each alkyl, cycloalkyl, cycloalkoxy, alkoxy, alkenyl,        alkynyl, phenyl, and phenoxy are optionally substituted with one        or more substituents independently selected from OH, F, Cl, Br,        I, CN, NO₂, oxo, C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₁-C₆        hydroxyalkyl, C₃-C₆ cycloalkyl, C₃-C₆ halocycloalkyl, C₃-C₆        hydroxycycloalkyl, C₃-C₆ cycloalkoxy, C₃-C₆ halocycloalkoxy,        C₃-C₆ hydroxycycloalkoxy, C₁-C₆ alkoxy, C₁-C₆ haloalkoxy, C₂-C₆        alkenyl, C₂-C₆ alkynyl, S(═O)(C₁-C₆ alkyl), S(═O)_(n)(C₁-C₆        haloalkyl), OSO₂(C₁-C₆ alkyl), OSO₂(C₁-C₆ haloalkyl),        C(═O)NR_(x)R_(y), (C₁-C₆ alkyl)NR_(x)R_(y), C(═O)(C₁-C₆ alkyl),        C(═O)O(C₁-C₆ alkyl), C(═O)(C₁-C₆ haloalkyl), C(═O)O(C₁-C₆        haloalkyl), C(═O)(C₃-C₆ cycloalkyl), C(═O)O(C₃-C₆ cycloalkyl),        C(═O)(C₂-C₆ alkenyl), C(═O)O(C₂-C₆ alkenyl), (C₁-C₆        alkyl)O(C₁-C₆ alkyl), (C₁-C₆ alkyl)S(C₁-C₆ alkyl), C(═O)(C₁-C₆        alkyl)C(═O)O(C₁-C₆ alkyl), phenyl, and phenoxy;

(f) R4 is H, CN, F, Cl, Br, I, C₁-C₆ alkyl, C₃-C₆ cycloalkyl, C₃-C₆cycloalkoxy, C₁-C₆ alkoxy, C₂-C₆ alkenyl, C₂-C₆ alkynyl, S(═O)_(n)(C₁-C₆alkyl), OSO₂(C₁-C₆ alkyl), OSO₂(C₁-C₆ haloalkyl), C(═O)NR_(x)R_(y),(C₁-C₆ alkyl)NR_(x)R_(y), C(═O)(C₁-C₆ alkyl), C(═O)O(C₁-C₆ alkyl),C(═O)(C₁-C₆ haloalkyl), C(═O)O(C₁-C₆ haloalkyl), C(═O)(C₃-C₆cycloalkyl), C(═O)O(C₃-C₆ cycloalkyl), C(═O)(C₂-C₆ alkenyl),C(═O)O(C₂-C₆ alkenyl), (C₁-C₆ alkyl)O(C₁-C₆ alkyl), (C₁-C₆ alkyl)S(C₁-C₆alkyl), C(═O)(C₁-C₆ alkyl)C(═O)O(C₁-C₆ alkyl), phenyl, and phenoxy,

-   -   wherein each alkyl, cycloalkyl, cycloalkoxy, alkoxy, alkenyl,        alkynyl, phenyl, and phenoxy are optionally substituted with one        or more substituents independently selected from OH, F, Cl, Br,        I, CN, NO₂, oxo, C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₁-C₆        hydroxyalkyl, C₃-C₆ cycloalkyl, C₃-C₆ halocycloalkyl, C₃-C₆        hydroxycycloalkyl, C₃-C₆ cycloalkoxy, C₃-C₆ halocycloalkoxy,        C₃-C₆ hydroxycycloalkoxy, C₁-C₆ alkoxy, C₁-C₆ haloalkoxy, C₂-C₆        alkenyl, C₂-C₆ alkynyl, S(═O)_(n)(C₁-C₆ alkyl), S(═O)_(n)(C₁-C₆        haloalkyl), OSO₂(C₁-C₆ alkyl), OSO₂(C₁-C₆ haloalkyl),        C(═O)NR_(x)R_(y), (C₁-C₆ alkyl)NR_(x)R_(y), C(═O)(C₁-C₆ alkyl),        C(═O)O(C₁-C₆ alkyl), C(═O)(C₁-C₆ haloalkyl), C(═O)O(C₁-C₆        haloalkyl), C(═O)(C₃-C₆ cycloalkyl), C(═O)O(C₃-C₆ cycloalkyl),        C(═O)(C₂-C₆ alkenyl), C(═O)O(C₂-C₆ alkenyl), (C₁-C₆        alkyl)O(C₁-C₆ alkyl), (C₁-C₆ alkyl)S(C₁-C₆ alkyl), C(═O)(C₁-C₆        alkyl)C(═O)O(C₁-C₆ alkyl), phenyl, and phenoxy;

(g) R5 is H, CN, F, Cl, Br, I, C₁-C₆ alkyl, C₃-C₆ cycloalkyl, C₃-C₆cycloalkoxy, C₁-C₆ alkoxy, C₂-C₆ alkenyl, C₂-C₆ alkynyl, S(═O)_(n)(C₁-C₆alkyl), OSO₂(C₁-C₆ alkyl), OSO₂(C₁-C₆ haloalkyl), C(═O)NR_(x)R_(y),(C₁-C₆ alkyl)NR_(x)R_(y), C(═O)(C₁-C₆ alkyl), C(═O)O(C₁-C₆ alkyl),C(═O)(C₁-C₆ haloalkyl), C(═O)O(C₁-C₆ haloalkyl), C(═O)(C₃-C₆cycloalkyl), C(═O)O(C₃-C₆ cycloalkyl), C(═O)(C₂-C₆ alkenyl),C(═O)O(C₂-C₆ alkenyl), (C₁-C₆ alkyl)O(C₁-C₆ alkyl), (C₁-C₆ alkyl)S(C₁-C₆alkyl), C(═O)(C₁-C₆ alkyl)C(═O)O(C₁-C₆ alkyl), Het, phenyl, and phenoxy,

-   -   wherein each alkyl, cycloalkyl, cycloalkoxy, alkoxy, alkenyl,        alkynyl, Het, phenyl, and phenoxy are optionally substituted        with one or more substituents independently selected from OH, F,        Cl, Br, I, CN, NO₂, oxo, C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₁-C₆        hydroxyalkyl, C₃-C₆ cycloalkyl, C₃-C₆ halocycloalkyl, C₃-C₆        hydroxycycloalkyl, C₃-C₆ cycloalkoxy, C₃-C₆ halocycloalkoxy,        C₃-C₆ hydroxycycloalkoxy, C₁-C₆ alkoxy, C₁-C₆ haloalkoxy, C₂-C₆        alkenyl, C₂-C₆ alkynyl, S(═O)_(n)(C₁-C₆ alkyl), S(═O)_(n)(C₁-C₆        haloalkyl), OSO₂(C₁-C₆ alkyl), OSO₂(C₁-C₆ haloalkyl),        C(═O)NR_(x)R_(y), (C₁-C₆ alkyl)NR_(x)R_(y), C(═O)(C₁-C₆ alkyl),        C(═O)O(C₁-C₆ alkyl), C(═O)(C₁-C₆ haloalkyl), C(═O)O(C₁-C₆        haloalkyl), C(═O)(C₃-C₆ cycloalkyl), C(═O)O(C₃-C₆ cycloalkyl),        C(═O)(C₂-C₆ alkenyl), C(═O)O(C₂-C₆ alkenyl), (C₁-C₆        alkyl)O(C₁-C₆ alkyl), (C₁-C₆ alkyl)S(C₁-C₆ alkyl), C(═O)(C₁-C₆        alkyl)C(═O)O(C₁-C₆ alkyl), NR_(x)R_(y), phenyl, and phenoxy;

(h) R6 is H, CN, F, Cl, Br, I, C₁-C₆ alkyl, C₃-C₆ cycloalkyl, C₃-C₆cycloalkoxy, C₁-C₆ alkoxy, C₂-C₆ alkenyl, C₂-C₆ alkynyl, S(═O)_(n)(C₁-C₆alkyl), OSO₂(C₁-C₆ alkyl), OSO₂(C₁-C₆ haloalkyl), C(═O)NR_(x)R_(y),(C₁-C₆ alkyl)NR_(x)R_(y), C(═O)(C₁-C₆ alkyl), C(═O)O(C₁-C₆ alkyl),C(═O)(C₁-C₆ haloalkyl), C(═O)O(C₁-C₆ haloalkyl), C(═O)(C₃-C₆cycloalkyl), C(═O)O(C₃-C₆ cycloalkyl), C(═O)(C₂-C₆ alkenyl),C(═O)O(C₂-C₆ alkenyl), (C₁-C₆ alkyl)O(C₁-C₆ alkyl), (C₁-C₆ alkyl)S(C₁-C₆alkyl), C(═O)(C₁-C₆ alkyl)C(═O)O(C₁-C₆ alkyl), phenyl, and phenoxy,

-   -   wherein each alkyl, cycloalkyl, cycloalkoxy, alkoxy, alkenyl,        alkynyl, phenyl, and phenoxy are optionally substituted with one        or more substituents independently selected from OH, F, Cl, Br,        I, CN, NO₂, oxo, C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₁-C₆        hydroxyalkyl, C₃-C₆ cycloalkyl, C₃-C₆ halocycloalkyl, C₃-C₆        hydroxycycloalkyl, C₃-C₆ cycloalkoxy, C₃-C₆ halocycloalkoxy,        C₃-C₆ hydroxycycloalkoxy, C₁-C₆ alkoxy, C₁-C₆ haloalkoxy, C₂-C₆        alkenyl, C₂-C₆ alkynyl, S(═O)_(n)(C₁-C₆ alkyl), S(═O)_(n)(C₁-C₆        haloalkyl), OSO₂(C₁-C₆ alkyl), OSO₂(C₁-C₆ haloalkyl),        C(═O)NR_(x)R_(y), (C₁-C₆ alkyl)NR_(x)R_(y), C(═O)(C₁-C₆ alkyl),        C(═O)O(C₁-C₆ alkyl), C(═O)(C₁-C₆ haloalkyl), C(═O)O(C₁-C₆        haloalkyl), C(═O)(C₃-C₆ cycloalkyl), C(═O)O(C₃-C₆ cycloalkyl),        C(═O)(C₂-C₆ alkenyl), C(═O)O(C₂-C₆ alkenyl), (C₁-C₆        alkyl)O(C₁-C₆ alkyl), (C₁-C₆ alkyl)S(C₁-C₆ alkyl), C(═O)(C₁-C₆        alkyl)C(═O)O(C₁-C₆ alkyl), Het, phenyl, and phenoxy;

(i) R7 is H, CN, F, Cl, Br, I, C₁-C₆ alkyl, C₃-C₆ cycloalkyl, C₃-C₆cycloalkoxy, C₁-C₆ alkoxy, C₂-C₆ alkenyl, C₂-C₆ alkynyl, S(═O)_(n)(C₁-C₆alkyl), OSO₂(C₁-C₆ alkyl), OSO₂(C₁-C₆ haloalkyl), C(═O)NR_(x)R_(y),(C₁-C₆ alkyl)NR_(x)R_(y), C(═O)(C₁-C₆ alkyl), C(═O)O(C₁-C₆ alkyl),C(═O)(C₁-C₆ haloalkyl), C(═O)O(C₁-C₆ haloalkyl), C(═O)(C₃-C₆cycloalkyl), C(═O)O(C₃-C₆ cycloalkyl), C(═O)(C₂-C₆ alkenyl),C(═O)O(C₂-C₆ alkenyl), (C₁-C₆ alkyl)O(C₁-C₆ alkyl), (C₁-C₆alkyl)OC(═O)(C₁-C₆ alkyl), (C₁-C₆ alkyl)S(C₁-C₆ alkyl), C(═O)(C₁-C₆alkyl)C(═O)O(C₁-C₆ alkyl), phenyl, and phenoxy,

-   -   wherein each alkyl, cycloalkyl, cycloalkoxy, alkoxy, alkenyl,        alkynyl, phenyl, and phenoxy are optionally substituted with one        or more substituents independently selected from OH, F, Cl, Br,        I, CN, NO₂, oxo, C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₁-C₆        hydroxyalkyl, C₃-C₆ cycloalkyl, C₃-C₆ halocycloalkyl, C₃-C₆        hydroxycycloalkyl, C₃-C₆ cycloalkoxy, C₃-C₆ halocycloalkoxy,        C₃-C₆ hydroxycycloalkoxy, C₁-C₆ alkoxy, C₁-C₆ haloalkoxy, C₂-C₆        alkenyl, C₂-C₆ alkynyl, S(═O)_(n)(C₁-C₆ alkyl), S(═O)_(n)(C₁-C₆        haloalkyl), OSO₂(C₁-C₆ alkyl), OSO₂(C₁-C₆ haloalkyl),        C(═O)NR_(x)R_(y), (C₁-C₆ alkyl)NR_(x)R_(y), C(═O)(C₁-C₆ alkyl),        C(═O)O(C₁-C₆ alkyl), C(═O)(C₁-C₆ haloalkyl), C(═O)O(C₁-C₆        haloalkyl), C(═O)(C₃-C₆ cycloalkyl), C(═O)O(C₃-C₆ cycloalkyl),        C(═O)(C₂-C₆ alkenyl), C(═O)O(C₂-C₆ alkenyl), (C₁-C₆        alkyl)O(C₁-C₆ alkyl), (C₁-C₆ alkyl)S(C₁-C₆ alkyl), C(═O)(C₁-C₆        alkyl)C(═O)O(C₁-C₆ alkyl), phenyl, and phenoxy;

(j) X1 is S or O;

(k) n=0, 1, or 2 (each independently); and

(l) R_(x) and R_(y) are independently selected from H, C₁-C₆ alkyl,C₁-C₆ haloalkyl, C₁-C₆ hydroxyalkyl, C₃-C₆ cycloalkyl, C₃-C₆halocycloalkyl, C₃-C₆ hydroxycycloalkyl, C₂-C₆ alkenyl, C₂-C₆ alkynyl,S(═O)_(n)(C₁-C₆ alkyl), S(═O)_(n)(C₁-C₆ haloalkyl), OSO₂(C₁-C₆ alkyl),OSO₂(C₁-C₆ haloalkyl), C(═O)H, C(═O)(C₁-C₆ alkyl), C(═O)O(C₁-C₆ alkyl),C(═O)(C₁-C₆ haloalkyl), C(═O)O(C₁-C₆ haloalkyl), C(═O)(C₃-C₆cycloalkyl), C(═O)O(C₃-C₆ cycloalkyl), C(═O)(C₂-C₆ alkenyl),C(═O)O(C₂-C₆ alkenyl), (C₁-C₆ alkyl)O(C₁-C₆ alkyl), (C₁-C₆ alkyl)S(C₁-C₆alkyl), C(═O)(C₁-C₆ alkyl)C(═O)O(C₁-C₆ alkyl), and phenyl.

In another embodiment Ar₁ is a substituted phenyl wherein saidsubstituted phenyl, has one or more substituents independently selectedfrom C₁-C₆ haloalkoxy.

In another embodiment Het is a triazolyl. In another embodiment Het is a1,2,4-triazolyl. In another embodiment Het is a 1,2,4-triazolyl with onering nitrogen atom bonded to Ar₁ and one ring carbon bonded to Ar₂.

In another embodiment Ar₂ is a phenyl.

In another embodiment R1 is H.

In another embodiment R2 is H.

In another embodiment R1, R2, and the carbons they are attached to forma cyclopropyl structure, in which case, R1 & R2 are the linking carbonatom.

In another embodiment R3 is H.

In another embodiment R4 is H. In another embodiment R4 is a phenyloptionally substituted with one or more substituents independentlyselected from C₁-C₆ alkyl.

In another embodiment R5 is Het or phenyl wherein each are optionallysubstituted with one or more substituents independently selected from F,Cl, C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₁-C₆ alkoxy, or NR_(x)R_(y).

In another embodiment R6 is C₁-C₆ alkyl or phenyl wherein each areoptionally substituted with one or more substituents independentlyselected from F, Cl, C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₃-C₆ cycloalkyl,C₁-C₆ alkoxy, Het, or phenyl.

In another embodiment R7 is (C₁-C₆ alkyl)OC(═O)(C₁-C₆ alkyl).

While these embodiments have been expressed, other embodiments andcombinations of these expressed embodiments and other embodiments arepossible.

The molecules of Formula One, Two, Three, and Four will generally have amolecular mass of about 100 Daltons to about 1200 Daltons. However, itis generally preferred if the molecular mass is from about 120 Daltonsto about 900 Daltons, and it is even more generally preferred if themolecular mass is from about 140 Daltons to about 600 Daltons.

EXAMPLES

The examples are for illustration purposes and are not to be construedas limiting the invention disclosed in this document to only theembodiments disclosed in these examples.

Starting materials, reagents, and solvents that were obtained fromcommercial sources were used without further purification unlessotherwise stated. Anhydrous solvents were purchased as Sure/Seal™ fromAldrich and were used as received. Melting points were obtained on aThomas Hoover Unimelt capillary melting point apparatus or an OptiMeltAutomated Melting Point System from Stanford Research Systems and areuncorrected. Molecules are given their known names, named according tonaming programs within ISIS Draw, ChemDraw or ACD Name Pro. If suchprograms are unable to name a molecule, the molecule is named usingconventional naming rules. ¹H NMR spectral data are in ppm (δ) and wererecorded at 300, 400 or 600 MHz, and ¹³C NMR spectral data are in ppm(δ) and were recorded at 75, 100 or 150 MHz, unless otherwise stated.

Compounds of this invention can be prepared by making a triarylintermediate, Ar₁-Het-Ar₂, and then linking it to the desiredintermediate to form the desired compound. A wide variety of triarylintermediates can be used to prepare compounds of this invention,provided that such triaryl intermediates contain a suitable functionalgroup on Ar₂ to which the rest of the desired intermediate can beattached. Suitable functional groups include an oxoalkyl or a formylgroup. These triaryl intermediates can be prepared by methods previouslydescribed in the chemical literature, including Crouse et al. PCT Int.Appl. Publ. WO2009/102736 A1.

Preparation of Cyclopropyl-Linked Compounds

Cyclopropyl-linked compounds of Formula One can be prepared from thecorresponding aryl aldehydes via reaction with t-butyldiethylphosphonoacetate and a base, such as sodium hydride (NaH), intetrahydrofuran (THF), at 0° C. The unsaturated ester is converted tothe cyclopropyl ester with trimethylsulfoxonium iodide in dimethylsulfoxide (DMSO) at ambient temperature. The cyclopropyl acyl azide Acan be prepared from the precursor ester in two steps by reaction firstwith trifluoroacetic acid (TFA) in dichloromethane (CH₂Cl₂) attemperatures from 0 to 25° C. and then with diphenylphosphorylazide(DPPA) and a base, such as triethylamine, in toluene at ambienttemperature. The acyl azide A is converted via Curtius rearrangementwith tert-butyl alcohol (t-BuOH) in toluene at 90° C. to the tert-butylcarbamate. The t-butyl carbamate is removed using TFA in dichloromethaneat temperatures from 0 to 25° C. to provide the trifluoroacetate salt ofthe amine B. The thioureas can be prepared from the salt B with anappropriately substituted isothiocyanate (R5-NCX1, wherein X1=S) in thepresence of a base, such as triethylamine, in THF at 80° C., or in atwo-step process, by first reacting the salt B with thiophosgene togenerate an isothiocyanate, which is allowed to react with anappropriately substituted amine (R4R5NH) Likewise, ureas can begenerated with an appropriately substituted isocyanate (R5-NCX1, whereinX1=0) in the presence of a base, such as triethylamine, in THF at 80° C.

Compounds of Formula Two may be synthesized by Curtius rearrangement ofacyl azide A and other alcohols ((R6)OH) with or without a base, such astriethylamine, at 100° C. Alternatively, the trifluoroacetate salt ofthe amine B can be allowed to react with substituted (R6) chloroformatesin the presence of a base to give the compounds of Formulas Two.

Compounds of Formula Three can be produced via alkylation of compoundsof Formula One with an alkyl halide (R7) in a non-reactive solvent suchas chloroform (CHCl₃) at 100° C.

Compounds of Formula Four can be generated by reaction of thecyclopropyl carboxylic acid DPPA and a base, such as triethylamine, int-BuOH at 90° C.

Example 1 Preparation of(E)-3-{4-[1-(4-trifluoromethoxyphenyl)-1H-[1,2,4]triazol-3-yl]phenyl}acrylicacid tert-butyl ester

Sodium hydride (NaH, 60% suspension in mineral oil; 440 milligrams (mg),11.0 millimoles (mmol)) was suspended in THF (20 milliliters (mL)), andthe mixture was cooled to 0° C. t-Butyl diethylphosphonoacetate (2.57mL; 11.0 mmol) was added over 2 minutes (min). The mixture was stirredat 0° C. for another 15 min, during which time the grey slurry turnedclear within 5 min.4-[1-(4-Trifluoromethoxyphenyl)-1H-[1,2,4]triazol-3-yl]-benzaldehyde(3.04 grams (g); 9.13 mmol) was suspended in THF (20 mL) and then addeddropwise via cannula to the solution above. The mixture was then warmedto 25° C., poured into saturated (satd) aqueous (aq) ammonium chloride(NH₄Cl; 200 mL), and extracted with 50% ethyl acetate (EtOAc)/hexanes(3×100 mL). The combined organic extracts were then dried over sodiumsulfate (Na₂SO₄) and concentrated in vacuo. The yellow solid residue wasdissolved in dichloromethane (CH₂Cl₂; 10 mL) and rapidly stirred ashexanes (100 mL) was added dropwise over 30 min. The light yellowcrystals were collected on a Büchner funnel and dried in vacuo to affordthe title compound ((2.93 g, 74%). The filtrate was concentrated invacuo and purified by chromatography on silica gel (gradient elutionwith 15% to 40% to 80% EtOAc in hexanes) to afford additional product(0.215 g, 5%): mp 167-169° C.; ¹H NMR (400 MHz, CDCl₃) δ 8.58 (s, 1H),8.20 (d, J=8.3 Hz, 2H), 7.80 (d, J=8.9 Hz, 2H), 7.63 (d, J=15.8 Hz, 1H),7.62 (d, J=8.5 Hz, 2H), 7.39 (d, J=8.6 Hz, 2H), 6.44 (d, J=16.0 Hz, 1H),1.54 (s, 9H); HRMS-ESI (m/z) [M]⁺ calcd for C₂₂H₂₀F₃N₃O₃, 431.146;found, 431.1457.

Example 2 Preparation of2-{4-[1-(4-trifluoromethoxyphenyl)-1H-[1,2,4]triazol-3-yl]phenyl}cyclopropanecarboxylicacid tert-butyl ester

NaH (60% suspension in mineral oil; 400 mg, 10.1 mmol) andtrimethylsulfoxonium iodide (2.22 g, 10 mmol) were charged into a roundbottom flask with a stir bar and placed in an ice bath. DMSO (20 mL) wasadded over a period of 10 min with vigorous stirring, and then theresulting grey slurry was warmed to 25° C. and stirred for 1 h, duringwhich time the slurry became clear. The enoate from Example 1 wasdissolved in DMSO (20 mL) and added to the above solution via cannulaover a period of 30 min DMSO (5 mL) was used to transfer any remainingmaterial from the flask. The resulting yellow-orange solution wasstirred at 25° C. for 2 h, then warmed to 50° C. and stirred for 3 h.The solution was then cooled back down to 25° C., stirred for another 12h, and poured into ice water (300 mL). The mixture was extracted with50% EtOAc/hexanes (3×150 mL), and the combined organic extracts werewashed with brine, dried over Na₂SO₄, and concentrated in vacuo to givea pale orange solid. Purification by silica gel chromatography (gradientelution with 15% to 40% to 80% EtOAc in hexanes) afforded the product(2.19 g, 73%) as a light pink solid: mp 100-101° C.; ¹H NMR (300 MHz,CDCl₃) δ 8.55 (s, 1H), 8.10 (d, J=8.4 Hz, 2H), 7.79 (d, J=9.1 Hz, 2H),7.38 (dd, J=9.0, 0.8 Hz, 2H), 7.19 (d, J=8.3 Hz, 2H), 2.49 (ddd, J=9.2,6.4, 4.2 Hz, 1H), 1.90 (ddd, J=8.4, 5.4, 4.2 Hz, 1H), 1.57 (ddd, J=9.9,9.2, 4.6 Hz, 1H), 1.48 (s, 9H), 1.29 (ddd, J=8.4, 6.4, 4.5 Hz, 1H);ESIMS m/z 446 (M+H).

Example 3 Preparation of2-{4-[1-(4-trifluoromethoxyphenyl)-1H-[1,2,4]triazol-3-yl]phenyl}cyclopropanecarbonylazide

Step 1. To a solution of the tert-butyl ester from Example 2 (0.562 g;1.26 mmol) in CH₂Cl₂ (8.0 mL) at 25° C. was added trifluoroacetic acid(TFA; 4.0 mL). The solution was stirred at 25° C. for 18 h and was thenconcentrated in vacuo to afford the carboxylic acid TFA salt (665 mg) asa light pink solid.

Step 2. Without further purification, a portion of this solid (558 mg,1.11 mmol) was slurried in toluene (PhCH₃; 3.2 mL). Triethylamine (Et₃N,0.368 mL, 2.66 mmol) was added, and the slurry clarified to give ayellow solution. Diphenylphosphoryl azide (DPPA; 0.287 mL, 1.33 mmol)was then added in one portion. The mixture was stirred for 2 h at 25°C., at which point analysis of an aliquot by liquid chromatography-massspectrometry (LC-MS) showed complete conversion to the product. Thecrude reaction mixture was directly applied to a silica gel column andpurified (gradient elution with 15% to 30% EtOAc in hexanes) to affordthe product (0.356 g, 78%) as a white solid: ¹H NMR (300 MHz, CDCl₃) δ8.54 (s, 1H), 8.10 (d, J=8.3 Hz, 2H), 7.78 (d, J=9.0 Hz, 2H), 7.37 (d,J=8.6 Hz, 2H), 7.18 (d, J=8.2 Hz, 2H), 2.68 (ddd, J=9.4, 6.8, 4.1 Hz,1H), 2.03-1.90 (m, 1H), 1.83-1.70 (m, 1H), 1.52 (ddd, J=8.3, 6.8, 4.7Hz, 1H); ESIMS m/z 387 (M+H).

Example 4 Preparation of(2-{4-[1-(4-trifluoromethoxyphenyl)-1H-[1,2,4]triazol-3-yl]phenyl}cyclopropyl)carbamicacid tert-butyl ester

2-{4-[1-(4-trifluoromethoxyphenyl)-1H-[1,2,4]triazol-3-yl]phenyl}cyclopropanecarbonylazide (0.301 g, 0.727 mmol) was slurried in PhCH₃ (2.0 mL). tert-Butylalcohol (t-BuOH; 0.250 mL, 2.64 mmol) was added, and the resultingmixture was heated at 90° C. for 24 h. During this time the slurrybecame homogenous to give a yellow solution. The mixture was cooled to25° C., and an off-white precipitate was observed to form. The slurrywas diluted with hexanes (3 mL) and filtered on a Büchner funnel toafford the product (0.252 g, 75%) as an off-white solid. The filtratewas concentrated in vacuo and purified by silica gel chromatography(gradient elution with 15% to 40% to 80% EtOAc in hexanes) to affordadditional product (0.0154 g, 5%): mp 169-172° C.; ¹H NMR (300 MHz,CDCl₃) δ 8.54 (s, 1H), 8.07 (d, J=8.1 Hz, 2H), 7.78 (d, J=8.9 Hz, 2H),7.37 (d, J=8.6 Hz, 2H), 7.21 (d, J=8.1 Hz, 2H), 4.91 (s, J=0.9 Hz, 1H),2.86-2.72 (m, 1H), 2.15-2.03 (m, 1H), 1.46 (s, 9H), 1.29-1.15 (m, 2H);ESIMS m/z 461 (M+H).

Example 5 Preparation of2-{4-[1-(4-trifluoromethoxyphenyl)-1H-[1,2,4]triazol-3-yl]phenyl}cyclopropylamine

The carbamate from Example 4 (0.249 g, 0.541 mmol) was slurried inCH₂Cl₂ (3.5 mL) at 25° C., and TFA (1.5 mL) was added. The solidsdissolved to give an orange solution. The mixture was stirred at 25° C.for 2 h and was then concentrated in vacuo to afford an orange oil. Thismaterial was carried forward without further purification. An analyticalsample was prepared by dissolving ca. 20 mg of the oil in CH₂Cl₂ (0.4mL) and adding Et₃N (0.007 mL, 0.05 mmol). After 1 h, a whiteprecipitate was observed to form. The solid was collected on a Büchnerfunnel and dried in vacuo to afford the pure amine in freebase form(10.5 mg) as a white solid: mp 149-152° C.; ¹H NMR (300 MHz,methanol-d₄) δ 9.15 (s, 1H), 8.09 (d, J=8.4 Hz, 2H), 8.02 (d, J=9.2 Hz,2H), 7.50 (dd, J=9.1, 0.8 Hz, 2H), 7.30 (d, J=8.3 Hz, 2H), 2.93 (ddd,J=7.9, 4.5, 3.6 Hz, 1H), 2.43 (ddd, J=10.1, 6.7, 3.6 Hz, 1H), 1.54-1.34(m, 2H); ESIMS m/z 361 (M+H).

Example 6 Preparation of1-phenyl-3-(2-{4-[1-(4-trifluoromethoxyphenyl)-1H-[1,2,4]triazol-3-yl]phenyl}cyclopropyl)thiourea(Compound 1)

The amine trifluoroacetate salt from Example 5 (0.064 g, 0.135 mmol) wasdissolved in THF (0.5 mL). Et₃N (0.037 mL, 0.27 mmol) was added,followed by phenyl isothiocyanate (0.020 mL, 0.15 mmol). The resultingdark yellow solution was heated to 80° C. and stirred for 4 h. Thesolution was cooled to 25° C., loaded directly onto a silica gel columnand purified (gradient elution with 15% to 40% to 80% EtOAc in hexanes)to afford the product (0.0222 g, 33%) as a yellow oil: IR ν_(max) 3380,3218 (br), 1617, 1598, 1518, 1497, 1448, 1356, 1326, 1264, 1221, 1168,1111, 1065, 986, 910, 851, 756, 732, 694 cm⁻¹; ¹H NMR (300 MHz, CDCl₃) δ8.56 (s, 1H), 8.11 (d, J=8.3 Hz, 2H), 7.90 (br s, 1H), 7.78 (d, J=9.0Hz, 2H), 7.46-7.32 (m, 5H), 7.31-7.21 (m, 5H), 3.10 (br s, 1H), 2.25 (brs, 1H), 1.51-1.30 (m, 2H); HRMS-ESI (m/z) [M]⁺ calcd for C₂₅H₂₀F₃N₅OS,495.134; found, 495.1341.

The following compounds were synthesized in accordance with Example 6above.

1-(2,6-Dichlorophenyl)-3-(2-{4-[1-(4-trifluoromethoxyphenyl)-1H-[1,2,4]triazol-3-yl]phenyl}cyclopropyl)thiourea(Compound 2)

The product was isolated as a yellow solid (0.021 g, 28%): mp 118-123°C.; ¹H NMR (300 MHz, CDCl₃) δ 8.56 (s, 1H), 8.10 (d, J=8.3 Hz, 2H), 7.78(d, J=9.1 Hz, 2H), 7.47-7.33 (m, 5H), 7.29-7.16 (m, 4H), 3.00 (br s,1H), 2.42 (br s, 1H), 1.57-1.42 (m, 2H); HRMS-ESI (m/z) [M]⁺ calcd forC₂₅H₁₈Cl₂F₃N₅OS, 563.056; found, 563.0562.

1-(4-Methoxy-2-methylphenyl)-3-(2-{4-[1-(4-trifluoromethoxyphenyl)-1H-[1,2,4]triazol-3-yl]phenyl}cyclopropyl)thiourea(Compound 3)

The product was isolated as a yellow solid (0.013 g, 18%): IR ν_(max)3377, 3220 (br), 2928, 2854, 1612, 1517, 1446, 1247, 1162, 1113, 1047,986, 909, 850, 731 cm⁻¹; ¹H NMR (300 MHz, CDCl₃) δ 8.55 (s, 1H), 8.09(d, J=8.3 Hz, 2H), 7.79 (d, J=9.1 Hz, 2H), 7.44 (br s, 1H), 7.38 (m,2H), 7.28 (br s, 2H), 7.17 (br s, 1H), 6.81 (br s, 1H), 6.78 (d, J=8.6,2.7 Hz, 1H), 5.80 (br s, 1H), 3.81 (s, 3H), 3.20 (br s, 1H), 2.25 (s,3H), 2.17 (br s, 1H), 1.29-1.22 (m, 2H); HRMS-ESI (m/z) [M]⁺ calcd forC₂₇H₂₄F₃N₅O₂S, 539.160; found, 539.1602.

1-(4-Chloro-2-methylphenyl)-3-(2-{4-[1-(4-trifluoromethoxyphenyl)-1H-[1,2,4]triazol-3-yl]phenyl}cyclopropyl)thiourea(Compound 4)

The product was isolated as an off-white oily foam (53.4 mg, 82%): IRν_(max) 3210 (br), 3029, 2978, 1728, 1518, 1492, 1446, 1354, 1327, 1264cm⁻¹; ¹H NMR (300 MHz, CDCl₃) δ 8.55 (s, 1H), 8.11 (d, J=8.3 Hz, 2H),7.78 (d, J=9.0 Hz, 2H), 7.51 (br s, 1H), 7.42-7.35 (m, 2H), 7.30-7.08(m, 6H), 3.10 (br s, 1H), 2.38-2.09 (app s, 4H), 1.55-1.29 (m, 2H);HRMS-ESI (m/z) [M]⁺ calcd for C₂₆H₂₁ClF₃N₅OS, 543.1107; found, 543.1109.

1-(2-Chlorophenyl)-3-(2-{4-[1-(4-trifluoromethoxyphenyl)-1H-[1,2,4]triazol-3-yl]phenyl}cyclopropyl)thiourea(Compound 5)

The product was isolated as a white solid (49.0 mg, 78%): mp 176-179°C.; ¹H NMR (300 MHz, CDCl₃) δ 8.56 (s, 1H), 8.12 (d, J=8.3 Hz, 2H), 8.02(br s, 1H), 7.79 (d, J=9.0 Hz, 2H), 7.43-7.35 (m, 3H), 7.31 (td, J=7.9,1.4 Hz, 1H), 7.25-7.10 (m, 4H), 6.81 (br s, 1H), 3.04 (br s, 1H),2.49-2.28 (m, 1H), 1.62-1.39 (m, 2H); HRMS-ESI (m/z) [M]⁺ calcd forC₂₅H₁₉ClF₃N₅OS, 529.0951; found, 529.0950.

1-(2,6-Diethylphenyl)-3-(2-{4-[1-(4-trifluoromethoxyphenyl)-1H-[1,2,4]triazol-3-yl]phenyl}cyclopropyl)thiourea(Compound 6)

The product was isolated as a light yellow oil (24.5 mg, 36%): IRν_(max) 3375, 3180 (br), 2971, 2937, 2876, 1518, 1326, 1264, 1168, 1111,1064, 986, 910, 851, 731 cm⁻¹; ¹H NMR (400 MHz, CDCl₃) δ 8.55 (s, 1H),8.09 (d, J=8.2 Hz, 2H), 7.79 (d, J=9.0 Hz, 2H), 7.41-7.36 (m, 2H),7.35-7.28 (m, 3H), 7.24-7.12 (m, 3H), 5.55 (s, 1H), 3.29-3.22 (m, 1H),2.73-2.52 (m, 4H), 2.13-2.05 (m, 1H), 1.41-1.09 (m, 8H); HRMS-ESI (m/z)[M]⁺ calcd for C₂₉H₂₈F₃N₅OS, 551.197; found, 551.1967.

1-(4-Dimethylaminophenyl)-3-(2-{4-[1-(4-trifluoromethoxyphenyl)-1H-[1,2,4]triazol-3-yl]phenyl}cyclopropyl)thiourea(Compound 7)

The product was isolated as a yellow-orange solid (47.8 mg, 75%): mp190.5-192.5° C.; ¹H NMR (300 MHz, CDCl₃) δ 8.54 (s, 1H), 8.09 (d, J=8.3Hz, 2H), 7.79 (d, J=9.0 Hz, 2H), 7.58 (s, 1H), 7.37 (d, J=9.0 Hz, 2H),7.27 (d, J=9.4 Hz, 2H), 7.10 (br d, J=7.5 Hz, 2H), 6.70 (d, J=9.0 Hz,2H), 6.10 (br s, 1H), 3.30-3.10 (m, 1H), 2.98 (s, 6H), 2.25-2.12 (m,1H), 1.47-1.18 (m, 2H); HRMS-ESI (m/z) [M]⁺ calcd for C₂₇H₂₅F₃N₆OS,538.1763; found, 538.1754.

1-(2-{4-[1-(4-Trifluoromethoxyphenyl)-1H-[1,2,4]triazol-3-yl]phenyl}-cyclopropyl)-3-(4-trifluoromethylphenyl)thiourea(Compound 8)

The product was isolated as a white foam (50.5 mg, 73%): IR ν_(max)3377, 3217 (br), 3027, 1617, 1518, 1446, 1417, 1327, 1267, 1223, 1167,1126, 1067, 1018, 987, 909, 841, 732 cm⁻¹; ¹H NMR (300 MHz, CDCl₃) δ8.57 (s, 1H), 8.15 (d, J=8.3 Hz, 2H), 7.94 (br s, 1H), 7.79 (d, J=9.0Hz, 2H), 7.67-7.56 (m, 4H), 7.39 (d, J=8.5 Hz, 2H), 7.24 (d, J=9.5 Hz,2H), 6.82 (br s, 1H), 2.98 (br s, 1H), 2.41-2.25 (m, 1H), 1.70-1.39 (m,2H); HRMS-ESI (m/z) [M]⁺ calcd for C₂₆H₁₉F₆N₅OS, 563.122; found,563.1217.

1-(2-{4-[1-(4-Trifluoromethoxyphenyl)-1H-[1,2,4]triazol-3-yl]phenyl}-cyclopropyl)-3-(2,4,6-trimethylphenyl)thiourea(Compound 9)

The product was isolated as a white foam (55.0 mg, 78%): IR ν_(max)3373, 3205 (br), 3025, 2922, 1616, 1517, 1492, 1262, 1221, 1166, 986,910, 852, 731 cm⁻¹; ¹H NMR (300 MHz, CDCl₃) δ 8.54 (s, 1H), 8.09 (d,J=7.8 Hz, 2H), 7.78 (d, J=9.0 Hz, 2H), 7.37 (d, J=8.5 Hz, 2H), 7.33-7.27(m, 2H), 7.24-7.13 (m, 1H), 6.96 (app s, 2H), 5.59 (s, 1H), 3.26 (br s,1H), 2.30 (s, 3H), 2.22 (s, 6H), 2.17-2.06 (m, 1H), 1.42-1.04 (m, 2H);HRMS-ESI (m/z) [M]⁺ calcd for C₂₈H₂₆F₃N₅OS, 537.181; found, 537.1812.

1-(2,4-Dimethoxyphenyl)-3-(2-{4-[1-(4-trifluoromethoxyphenyl)-1H-[1,2,4]triazol-3-yl]phenyl}cyclopropyl)thiourea(Compound 10)

The product was isolated as a light yellow foam (58.2 mg, 69%): IRν_(max) 3357, 3204 (br), 2976, 2838, 1619, 1549, 1517, 1495, 1460, 1262,1208, 1182, 1159, 1047, 1031, 985 cm⁻¹; ¹H NMR (400 MHz, CDCl₃) δ 8.56(s, 1H), 8.50-7.60 (br, 2H), 8.11 (d, J=8.3 Hz, 2H), 7.79 (d, J=9.1 Hz,2H), 7.38 (d, J=8.9 Hz, 2H), 7.24 (d, J=7.8 Hz, 1H), 6.40-6.90 (br m,2H), 6.50 (dd, J=8.8, 2.6 Hz, 1H), 6.44 (s, 1H), 3.79 (s, 3H), 3.62 (brs, 3H), 3.05 (br s, 1H), 2.29 (br s, 1H), 1.50-1.35 (m, 2H); HRMS-ESI(m/z) [M]⁺ calcd for C₂₇H₂₄F₃N₅O₃S, 555.1552; found, 555.156.

Example 7 Preparation of3-(4-(2-isothiocyanatocyclopropyl)phenyl)-1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazole

Thiophosgene (0.173 mL, 2.256 mmol) was added to a rapidly stirredmixture of CH₂Cl₂ (11 mL) and satd aq NaHCO₃ (11 mL) at 25° C. The aminetrifluoroacetate salt from Example 5 (1.07 g, 2.256 mmol) was thenadded, and stirring was continued for 10 min, during which time thesolids completely dissolved. The layers were separated, the aqueousphase was extracted with CH₂Cl₂, and the combined organic extracts wereconcentrated to afford the isothiocyanate as a yellow solid (0.86 g,95%): mp 99-104° C.; ¹H NMR (400 MHz, CDCl₃) δ 8.55 (s, 1H), 8.12 (d,J=8.4 Hz, 2H), 7.79 (d, J=9.1 Hz, 2H), 7.38 (dd, J=9.0, 0.7 Hz, 2H),7.16 (d, J=8.2 Hz, 2H), 3.05 (ddd, J=7.5, 4.3, 3.3 Hz, 1H), 2.49 (ddd,J=10.1, 7.0, 3.2 Hz, 1H), 1.56 (ddd, J=10.0, 6.3, 4.3 Hz, 1H), 1.47-1.37(m, 1H); ESIMS m/z 403 (M+H).

Example 8 Preparation of1-(2,4-Dimethylphenyl)-3-(2-(4-(1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)phenyl)cyclopropyl)thiourea(Compound 11)

The isothiocyanate from Example 7 (50 mg, 0.124 mmol) was dissolved indioxane (0.35 mL) at 25° C., and 2,4-dimethylaniline (16.6 mg, 0.137mmol) was added in one portion. The mixture was stirred at 25° C. for 20h and was then concentrated in vacuo. Silica gel chromatography(gradient elution with 10% to 50% to 100% EtOAc in hexanes) provided thetitle compound (43.3 mg, 67%) as a light yellow oil: IR ν_(max) 3379,3215, 3025, 1616, 1446, 1517, 1326, 1262, 1165, 1111, 1064, 986, 909,850, 731 cm⁻¹; ¹H NMR (400 MHz, CDCl₃) δ 8.55 (s, 1H), 8.10 (d, J=8.3Hz, 2H), 7.79 (d, J=9.0 Hz, 2H), 7.46 (s, 1H), 7.38 (dd, J=9.0, 0.7 Hz,2H), 7.33-7.22 (m, 2H), 7.21-7.01 (m, 3H), 3.19 (br s, 1H), 2.34 (s,3H), 2.24 (s, 3H), 2.20 (br s, 1H), 1.40 (br s, 1H), 1.34-1.21 (m, 2H);HRMS-ESI (m/z) [M]⁺ calcd for C₂₇H₂₄F₃N₅OS, 523.1654; found, 523.1653.

The following compounds were synthesized in accordance with Example 8.

1-(2,6-Dimethylphenyl)-3-(2-(4-(1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)phenyl)cyclopropyl)thiourea(Compound 12)

The reaction mixture was heated at 100° C. for 12 h, and the product wasisolated as a tan foam (26.9 mg, 41%): IR ν_(max) 3372, 3208, 3032,2976, 2916, 2143, 1617, 1517, 1493, 1445, 1326, 1262, 1167, 1111, 1064cm⁻¹; ¹H NMR (400 MHz, CDCl₃, data for major rotamer) δ 8.55 (s, 1H),8.08 (d, J=7.4 Hz, 2H), 7.78 (d, J=9.0 Hz, 2H), 7.58 (br s, 1H), 7.37(d, J=8.3 Hz, 2H), 7.34-7.08 (m, 5H), 5.58 (br s, 1H), 3.26 (br, 1H),2.28 (s, 6H), 2.11 (br s, 1H), 1.34 (s, 1H), 1.18 (s, 1H); HRMS-ESI(m/z) [M]⁺ calcd for C₂₇H₂₄F₃N₅OS, 523.1654; found, 523.1653.

1-(2-Isopropyl-4-methoxyphenyl)-3-(2-(4-(1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)phenyl)cyclopropyl)thiourea(Compound 13)

The reaction mixture was stirred at 25° C. for 4 h, and the product wasisolated as a lavender solid via filtration of the reaction mixture (43mg, 51%): mp 130-134° C.; ¹H NMR (400 MHz, CDCl₃) δ 8.54 (s, 1H), 8.10(d, J=8.3 Hz, 2H), 7.79 (d, J=9.0 Hz, 2H), 7.44-7.34 (m, 3H), 7.28 (d,J=7.9 Hz, 2H), 7.21-7.10 (m, 1H), 6.89 (d, J=2.6 Hz, 1H), 6.78 (dd,J=8.6, 2.9 Hz, 1H), 5.78 (br, 1H), 3.83 (s, 3H), 3.21 (br s, 1H),3.14-3.03 (m, 1H), 2.16 (br s, 1H), 1.42-1.32 (m, 1H), 1.30-1.17 (m,1H), 1.20 (d, J=6.9 Hz, 3H), 1.19 (d, J=6.9 Hz, 3H); HRMS-ESI (m/z) [M]⁺calcd for C₂₉H₂₈F₃N₅O₂S, 567.1916; found, 567.1928.

1-(6-Methoxy-2,4-dimethylpyridin-3-yl)-3-(2-(4-(1-(4-(trifluoromethoxy)-phenyl)-1H-1,2,4-triazol-3-yl)phenyl)cyclopropyl)thiourea(Compound 14)

The reaction mixture was stirred for 20 h at 25° C., and the product wasisolated as an off-white solid (59.6 mg, 72%): mp 182-188° C.; ¹H NMR(400 MHz, CDCl₃, mixture of rotamers) δ 8.54 (s, 1H), 8.10 (br d, J=6.1Hz, 2H), 7.78 (d, J=9.0 Hz, 2H), 7.38 (d, J=8.3 Hz, 2H), 7.35-7.05 (m,4H), 6.51 (br s, 1H), 5.57 (br s, 0.5H), 3.91 (s, 3H), 3.48-3.21 (m,0.5H), 2.93 (dd, J=8.6, 5.1 Hz, 0.5H), 2.39 (br s, 3H), 2.21 (br s, 3H),2.12 (br, 0.5H), 1.64-1.46 (br, 1H), 1.43-1.32 (br, 0.5H), 1.25-1.10(br, 0.5H); HRMS-ESI (m/z) [M]⁺ calcd for C₂₇H₂₅F₃N₆O₂S, 554.1712;found, 554.1727.

Example 9 Preparation of(Z)-(N′-(2,6-dimethylphenyl)-N-(2-(4-(1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)phenyl)cyclopropyl)-carbamimidoylthio)methylisobutyrate (Compound 15)

To a solution of1-(2,6-dimethylphenyl)-3-(2-(4-(1-(4-(trifluoromethoxy)-phenyl)-1H-1,2,4-triazol-3-yl)phenyl)cyclopropyl)thiourea(75 mg, 0.143 mmol) in chloroform (CHCl₃; 0.72 mL) was addedchloromethyl isobutyrate (31.1 mg, 0.172 mmol). The mixture was heatedat 100° C. for 1 h. The mixture was cooled to 25° C., and the residuewas purified by silica gel chromatography (EtOAc-hexanes gradient) toafford the title compound (17.3 mg, 19%) as a yellow oil: IR ν_(max)3332 (br), 3124, 2976, 2939, 1739, 1631, 1590, 1518, 1264, 1171, 986cm⁻¹; ¹H NMR (400 MHz, CDCl₃) δ 8.54 (s, 1H), 8.09 (d, J=8.3 Hz, 2H),7.79 (d, J=9.0 Hz, 2H), 7.37 (d, J=8.3 Hz, 2H), 7.20 (d, J=7.2 Hz, 2H),7.02 (d, J=7.5 Hz, 2H), 6.88 (t, J=7.5 Hz, 1H), 5.65 (br s, 2H), 2.88(br s, 1H), 2.68-2.52 (m, 1H), 2.10 (s, 6H), 1.82-1.46 (m, 2H),1.46-1.22 (m, 2H), 1.22-1.18 (m, 6H); ESIMS m/z 624 (M+H).

The following compound was synthesized in accordance with Example 9.

(Z)-(N′-Mesityl-N-(2-(4-(1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)phenyl)cyclopropyl)carbamimidoylthio)methylisobutyrate (Compound 16)

The product was isolated as a reddish-brown foam (48.3 mg, 20%): IRν_(max) 2974, 2921, 1739, 1612, 1515, 1298, 1205, 1163, 1053, 1025,1006, 985, 852, 818, 755 cm⁻¹; ¹H NMR (600 MHz, DMSO-d₆, 100° C.) δ 9.22(s, 1H), 8.03 (d, J=9.0 Hz, 2H), 7.99 (d, J=8.2 Hz, 2H), 7.55 (d, J=8.9Hz, 2H), 7.24 (d, J=8.0 Hz, 2H), 6.78 (s, 2H), 5.55 (s, 2H), 2.60-2.52(m, 1H), 2.26-2.12 (m, 1H), 2.18 (s, 3H), 2.04 (s, 6H), 1.55-1.34 (m,1H), 1.32-1.22 (m, 1H), 1.13 (d, J=7.0 Hz, 3H), 1.12 (d, J=7.0 Hz, 3H);ESIMS m/z 638 (M+H).

Example 10 tert-Butyl2-(4-(1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)phenyl)-cyclopropylcarbamate(Compound 17)

2-{4-[1-(4-trifluoromethoxyphenyl)-1H-[1,2,4]triazol-3-yl]phenyl}cyclopropanecarbonylazide (0.301 g, 0.727 mmol) was slurried in PhCH₃ (2.0 mL). tert-Butylalcohol (t-BuOH; 0.250 mL, 2.64 mmol) was added, and the resultingmixture was heated at 90° C. for 24 h. During this time the slurrybecame homogenous to give a yellow solution. The mixture was cooled to25° C., and an off-white precipitate was observed to form. The slurrywas diluted with hexanes (3 mL) and filtered on a Büchner funnel toafford the title compound (0.252 g, 75%) as an off-white solid. Thefiltrate was concentrated in vacuo and purified by silica gelchromatography (gradient elution with 15% to 40% to 80% EtOAc inhexanes) to afford additional product (0.0154 g, 5%): mp 169-172° C.; ¹HNMR (300 MHz, CDCl₃) δ 8.54 (s, 1H), 8.07 (d, J=8.1 Hz, 2H), 7.78 (d,J=8.9 Hz, 2H), 7.37 (d, J=8.6 Hz, 2H), 7.21 (d, J=8.1 Hz, 2H), 4.91 (s,J=0.9 Hz, 1H), 2.86-2.72 (m, 1H), 2.15-2.03 (m, 1H), 1.46 (s, 9H),1.29-1.15 (m, 2H); ESIMS m/z 461 (M+H).

The following compounds were synthesized in accordance with Example 10.

Methyl2-(4-(1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)phenyl)cyclopropyl-carbamate(Compound 18)

The product was isolated as an off-white solid (43.6 mg, 74%): mp227-228.5° C.; ¹H NMR (400 MHz, DMSO-d₆) δ 9.38 (s, 1H), 8.06 (d, J=9.0Hz, 2H), 7.99 (d, J=8.2 Hz, 2H), 7.61 (d, J=8.6 Hz, 2H), 7.24 (d, J=8.3Hz, 2H), 3.54 (s, 3H), 2.82-2.38 (m, 1H), 2.00 (td, J=7.7, 2.5 Hz, 1H),1.26-1.13 (m, 2H); HRMS-ESI (m/z) [M]⁺ calcd for C₂₀H₁₇F₃N₄O₃, 418.125;found, 418.1252.

1-Phenylethyl2-(4-(1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)phenyl)-cyclopropylcarbamate(Compound 19)

The product was purified by silica gel chromatography (EtOAc-hexanesgradient) and isolated as a light yellow solid (73.7 mg, 66%): mp125-137° C.; ¹H NMR (400 MHz, CDCl₃, 1:1 dr) δ 8.55 (s, 1H), 8.08 (d,J=8.3 Hz, 2H), 7.79 (d, J=9.0 Hz, 2H), 7.44-7.12 (m, 9H), 5.85 (q, J=6.6Hz, 1H), 5.08 (s, 1H), 2.87-2.77 (m, 1H), 2.20-2.05 (m, 1H), 1.56(diastereomer A, d, J=4.7 Hz, 1.5H), 1.54 (diastereomer B, d, J=4.7 Hz,1.5H), 1.41-1.15 (m, 2H); ESIMS m/z 510 (M+H).

1-(Pyridin-2-yl)ethyl2-(4-(1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)phenyl)-cyclopropylcarbamate(Compound 20)

The product was purified by silica gel chromatography (EtOAc-hexanesgradient) and isolated as a light yellow solid (83.6 mg, 73%). mp122-130° C. ¹H NMR (400 MHz, CDCl₃, 3:2 dr, data for major diastereomer)δ 8.59 (d, J=3.4 Hz, 1H), 8.55 (s, 1H), 8.08 (d, J=8.3 Hz, 2H), 7.79 (d,J=8.9 Hz, 2H), 7.67 (s, 1H), 7.43-7.35 (m, 2H), 7.35-7.29 (m, 1H),7.25-7.13 (m, 3H), 5.88 (q, J=6.6 Hz, 1H), 5.22 (br s, 1H), 2.84 (br s,1H), 2.28-2.06 (m, 1H), 1.61 (d, J=6.2 Hz, 3H), 1.40-1.15 (m, 2H); ESIMSm/z 511 (M+H).

Example 11 Phenyl2-(4-(1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)phenyl)cyclopropyl-carbamate(Compound 21)

2-{4-[1-(4-trifluoromethoxyphenyl)-1H-[1,2,4]triazol-3-yl]phenyl}cyclopropanecarbonylazide (75 mg, 0.18 mmol, 1.0 equiv) was slurried in PhCH₃ (0.52 mL, 0.35M). Phenol (18.7 mg, 0.199 mmol, 1.1 equiv) was added, and the resultingmixture was heated at 100° C. for 2 h. During this time the slurryhomogenized to give a yellow solution. The mixture was then cooled to25° C. and Et₃N (32.8 μL, 0.235 mmol, 1.3 equiv) was added. An off-whiteprecipitate was observed to form. The mixture was diluted with 20% EtOAcin hexanes, and the product was collected by vacuum filtration to affordthe title compound (62.9 mg, 72%) as an off-white solid: mp 171-173° C.;¹H NMR (400 MHz, CDCl₃) δ 8.54 (s, 1H), 8.09 (d, J=8.3 Hz, 2H), 7.79 (d,J=9.0 Hz, 2H), 7.44-7.31 (m, 4H), 7.28 (d, J=7.7 Hz, 2H), 7.21 (t, J=7.4Hz, 1H), 7.15 (d, J=7.9 Hz, 2H), 5.42 (s, 1H), 2.90 (s, 1H), 2.27 (ddd,J=9.6, 6.6, 3.2 Hz, 1H), 1.27-1.04 (m, 2H); ESIMS m/z 480 (M+H).

The following compounds were synthesized in accordance with Example 11.

4-Fluoro-2-methylphenyl2-(4-(1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)-phenyl)cyclopropylcarbamate(Compound 22)

The product was isolated as an off-white solid (58.7 mg, 63%): mp172-175° C.; ¹H NMR (400 MHz, CDCl₃) δ 8.55 (s, 1H), 8.09 (d, J=8.3 Hz,2H), 7.78 (d, J=9.0 Hz, 2H), 7.44-7.35 (m, 2H), 7.35-7.21 (m, 2H), 7.04(dd, J=8.1, 5.0 Hz, 1H), 6.95-6.81 (m, 2H), 5.46 (s, 1H), 3.16-2.67 (m,1H), 2.28 (dd, J=6.4, 3.2 Hz, 1H), 2.21 (s, 3H), 1.46-1.23 (m, 2H);ESIMS m/z 513 (M+H).

2-Cyclopentylphenyl2-(4-(1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)phenyl)-cyclopropylcarbamate(Compound 23)

The product was purified by silica gel chromatography (EtOAc-hexanesgradient) and isolated as a white solid (64.9 mg, 63%): mp 187-189° C.;¹H NMR (400 MHz, CDCl₃, data for major rotamer) δ 8.54 (s, 1H), 8.09 (d,J=8.3 Hz, 2H), 7.79 (d, J=9.0 Hz, 2H), 7.41-7.34 (m, 2H), 7.33-7.27 (m,3H), 7.22-7.14 (m, 2H), 7.11-7.04 (m, 1H), 5.44 (br s, 1H), 3.26-3.10(m, 1H), 2.91 (br s, 1H), 2.26 (ddd, J=9.5, 6.6, 3.2 Hz, 1H), 2.01 (brs, 2H), 1.79 (br s, 2H), 1.72-1.53 (m, 4H), 1.41-1.28 (m, 2H); ESIMS m/z550 (M+H).

2-tert-Butylphenyl2-(4-(1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)phenyl)-cyclopropylcarbamate(Compound 24)

The product was purified by silica gel chromatography (EtOAc-hexanesgradient) and isolated as a white solid (70.5 mg, 67%): mp 143.5-145.0°C.; ¹H NMR (400 MHz, CDCl₃, data for major rotamer) δ 8.54 (s, 1H), 8.09(d, J=8.2 Hz, 2H), 7.79 (d, J=9.0 Hz, 2H), 7.42-7.36 (m, 3H), 7.29 (d,J=7.7 Hz, 2H), 7.23 (td, J=7.6, 1.6 Hz, 1H), 7.15 (td, J=7.6, 1.5 Hz,1H), 7.09 (d, J=7.6 Hz, 1H), 5.46 (s, 1H), 2.93 (s, 1H), 2.32-2.21 (m,1H), 1.42-1.28 (m, 2H), 1.39 (s, 9H); ESIMS m/z 538 (M+H).

2-(Trifluoromethyl)phenyl2-(4-(1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)-phenyl)cyclopropylcarbamate(Compound 25)

The product was isolated as an off-white solid (66.9 mg, 46%). Thefiltrate was concentrated in vacuo and purified by silica gelchromatography (EtOAc-hexanes gradient) to afford additional product(26.2 mg, 20%): mp 183-187° C.; ¹H NMR (400 MHz, CDCl₃, data for majorrotamer) δ 8.54 (s, 1H), 8.09 (d, J=8.3 Hz, 2H), 7.79 (d, J=9.0 Hz, 2H),7.65 (d, J=7.7 Hz, 1H), 7.61-7.53 (m, 1H), 7.45-7.06 (m, 6H), 5.59 (s,1H), 3.03-2.80 (m, 1H), 2.37-2.21 (m, 1H), 1.43-1.29 (m, 2H); ESIMS m/z549 (M+H).

Example 12 Mesityl2-(4-(1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)phenyl)cyclopropyl-carbamate(Compound 26)

Step 1. 2,4,6-trimethylphenol (272 mg, 2.00 mmol, 1.0 equiv) wasdissolved in CH₂Cl₂ (3.33 mL, 0.3 M) under nitrogen (N₂) and cooled to0° C. Triphosgene (208 mg, 0.700 mmol, 0.35 equiv) was dissolved inCH₂Cl₂ (3.33 mL) and added dropwise, followed by pyridine (0.162 mL,2.00 mmol, 1.0 equiv). The mixture was allowed to warm to 25° C. over 18h, at which point the reaction was quenched with 10 mL 1 normal (N)hydrochloric acid (HCl; aq) and extracted with EtOAc. The organic layerwas washed with 1 N HCl (aq), dried over Na₂SO₄, and concentrated togive mesityl chloroformate as an oil (88% purity by ¹H NMRspectroscopy). The chloroformate so prepared was used directly in thenext step without further purification.

Step 2.2-{4-[1-(4-trifluoromethoxyphenyl)-1H-[1,2,4]triazol-3-yl]phenyl}cyclopropylamine(46.0 mg, 0.13 mmol, 1.0 equiv) was dissolved in CH₂Cl₂ (0.55 mL) underN₂. 4-Dimethylaminopyridine (DMAP; 0.8 mg, 0.006 mmol, 0.05 equiv) andEt₃N (27 μL, 0.19 mmol, 1.5 equiv) were added, followed by mesitylchloroformate prepared above (33 mg, 0.17 mmol, 1.2 equiv). The reactionwas stirred for 5 min and was then quenched with NaHCO₃ (aq). The layerswere separated, and the aqueous layer was extracted twice more withCH₂Cl₂. The combined organic extracts were concentrated, and the crudeproduct was purified by silica gel chromatography (EtOAc-hexanesgradient) to afford the title compound as a white solid (53.0 mg, 79%):mp 199-202° C.; ¹H NMR (400 MHz, CDCl₃, data for major rotamer) δ 8.54(s, 1H), 8.08 (d, J=8.3 Hz, 2H), 7.78 (d, J=9.0 Hz, 2H), 7.39 (d, J=0.7Hz, 2H), 7.32-7.21 (m, 2H), 6.86 (s, 2H), 5.71-5.36 (m, 0.7H), 5.22-4.82(m, 0.3H), 3.09-2.81 (m, 1H), 2.26 (s, 4H), 2.17 (s, 6H), 1.43-1.26 (m,2H); ESIMS m/z 523 (M+H).

The following compounds were synthesized in accordance with Example 12.

4-Methoxyphenyl2-(4-(1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)phenyl)-cyclopropylcarbamate(Compound 27)

The product was isolated as a white solid (60.0 mg, 66%): mp 163-164°C.; ¹H NMR (400 MHz, CDCl₃) δ 8.54 (s, 1H), 8.09 (d, J=8.3 Hz, 2H), 7.79(d, J=9.0 Hz, 2H), 7.38 (dd, J=9.0, 0.7 Hz, 2H), 7.29 (d, J=7.9 Hz, 2H),7.06 (d, J=8.9 Hz, 2H), 6.88 (d, J=9.1 Hz, 2H), 5.35 (s, 1H), 3.80 (s,3H), 2.89 (s, 1H), 2.27 (ddd, J=9.6, 6.6, 3.2 Hz, 1H), 1.40-1.26 (m,2H); ESIMS m/z 511 (M+H), 509 (M−H).

2,6-Dichlorophenyl2-(4-(1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)phenyl)-cyclopropylcarbamate(Compound 28)

The product was isolated as a white solid (26.1 mg, 33%): mp 160-162°C.; ¹H NMR (400 MHz, CDCl₃, data for major rotamer) δ 8.54 (s, 1H), 8.09(d, J=8.3 Hz, 2H), 7.79 (d, J=9.0 Hz, 2H), 7.38 (d, J=8.1 Hz, 2H), 7.35(d, J=8.2 Hz, 2H), 7.28 (d, J=8.0 Hz, 2H), 7.13 (t, J=8.1 Hz, 1H), 5.62(s, 1H), 2.94 (s, 1H), 2.31 (s, 1H), 1.46-1.28 (m, 2H); ESIMS m/z 550(M+H).

2-Isopropylphenyl2-(4-(1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)phenyl)-cyclopropylcarbamate(Compound 29)

The product was isolated as a white solid (52.8 mg, 63%): mp 186-188°C.; ¹H NMR (400 MHz, CDCl₃, data for major rotamer) δ 8.54 (s, 1H), 8.09(d, J=8.3 Hz, 2H), 7.79 (d, J=9.0 Hz, 2H), 7.44-7.34 (m, 2H), 7.33-7.26(m, 2H), 7.23-7.16 (m, 2H), 7.13-7.05 (m, 1H), 5.43 (br s, 1H),3.19-3.07 (m, 1H), 2.91 (br s, 1H), 2.27 (ddd, J=9.5, 6.7, 3.1 Hz, 1H),1.42-1.33 (m, 2H), 1.22 (br d, J=6.1 Hz, 3H); ESIMS m/z 523 (M+H).

Example 131-Mesityl-3-(2-(4-(1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)phenyl)-cyclopropyl)urea(Compound 30)

2-{4-[1-(4-trifluoromethoxyphenyl)-1H-[1,2,4]triazol-3-yl]phenyl}cyclopropylaminetrifluoroacetate salt (58 mg, 0.12 mmol, 1.0 equiv) was dissolved in THF(0.60 mL, 0.20 M) at 25° C. under N₂. The isocyanate (22 mg, 0.13 mmol,1.1 equiv) was added in one portion, followed by Et₃N (19 μL, 0.13 mmol,1.1 equiv). The mixture was stirred at 25° C. for 1 h, and then methylalcohol-water (1:1) was added. The precipitate was collected by vacuumfiltration and rinsed with methyl alcohol to afford the title compoundas a white solid (41.3 mg, 65%): mp 254-256° C.; ¹H NMR (300 MHz,DMSO-d₆) δ 9.35 (s, 1H), 8.04 (d, J=9.0 Hz, 2H), 7.97 (d, J=8.3 Hz, 2H),7.59 (d, J=8.5 Hz, 2H), 7.32 (s, 1H), 7.22 (d, J=8.3 Hz, 2H), 6.82 (s,2H), 6.48 (s, 1H), 2.87-2.73 (m, 1H), 2.19 (s, 3H), 2.10 (s, 6H),2.06-1.95 (m, 1H), 1.28-1.11 (m, 2H); ESIMS m/z 522 (M+H).

The following compound was synthesized in accordance with Example 13.

1-(2,6-Dichlorophenyl)-3-(2-(4-(1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)phenyl)cyclopropyl)urea(Compound 31)

The product was isolated as a white solid (44.6 mg, 80%): mp215.5-217.5° C.; ¹H NMR (300 MHz, DMSO-d₆) δ 9.35 (s, 1H), 8.05 (d,J=9.1 Hz, 2H), 7.98 (app d, J=8.1 Hz, 3H), 7.61 (s, 2H), 7.47 (d, J=8.0Hz, 2H), 7.32-7.22 (m, 3H), 6.87 (d, J=3.2 Hz, 1H), 2.88-2.66 (m, 1H),2.13-1.96 (m, 1H), 1.31-1.14 (m, 2H); ESIMS m/z 549 (M+H), 547 (M−H).

Example 14 Preparation of1,3-bis(2-(4-(1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)phenyl)cyclopropyl)urea(Compound 32)

Step 2 in Example 3 was carried out using t-butyl alcohol as solventinstead of PhCH₃. The mixture was heated at 90° C. for 3 h, cooled to25° C., and diluted with 1:1 t-butyl alcohol-water. The mixture was thenfiltered to afford the title compound (202.2 mg, 93%) as an off-whitesolid. The intended product (the t-butyl carbamate) was not isolated: mp232-234° C. dec; ¹H NMR (300 MHz, DMSO-d₆) δ 9.37 (s, 2H), 8.06 (d,J=9.0 Hz, 4H), 7.99 (d, J=8.2 Hz, 4H), 7.61 (d, J=8.8 Hz, 4H), 7.23 (d,J=8.3 Hz, 4H), 6.39 (d, J=3.0 Hz, 2H), 2.89-2.66 (m, 2H), 2.12-1.89 (m,2H), 1.25-1.07 (m, 4H); ESIMS m/z 747 (M+H).

Example 15 Bioassays on Beet Armyworm (“BAW”) and Corn Earworm (“CEW”)

BAW has few effective parasites, diseases, or predators to lower itspopulation. BAW infests many weeds, trees, grasses, legumes, and fieldcrops. In various places, it is of economic concern upon asparagus,cotton, corn, soybeans, tobacco, alfalfa, sugar beets, peppers,tomatoes, potatoes, onions, peas, sunflowers, and citrus, among otherplants. CEW is known to attack corn and tomatoes, but it also attacksartichoke, asparagus, cabbage, cantaloupe, collards, cowpeas, cucumbers,eggplant, lettuce, lima beans, melon, okra, peas, peppers, potatoes,pumpkin, snap beans, spinach, squash, sweet potatoes, and watermelon,among other plants. CEW is also known to be resistant to certaininsecticides. Consequently, because of the above factors control ofthese pests is important. Furthermore, molecules that control thesepests are useful in controlling other pests.

Certain molecules disclosed in this document were tested against BAW andCEW using procedures described in the following examples. In thereporting of the results, the “BAW & CEW Rating Table” was used (SeeTable Section).

Bioassays on BAW (Spodoptera exigua)

Bioassays on BAW were conducted using a 128-well diet tray assay. One tofive second instar BAW larvae were placed in each well (3 mL) of thediet tray that had been previously filled with 1 mL of artificial dietto which 50 μg/cm² of the test compound (dissolved in 50 μL of 90:10acetone-water mixture) had been applied (to each of eight wells) andthen allowed to dry. Trays were covered with a clear self-adhesivecover, and held at 25° C., 14:10 light-dark for five to seven days.Percent mortality was recorded for the larvae in each well; activity inthe eight wells was then averaged. The results are indicated in thetable entitled “Table: Bio Results” (See Table Section).

Bioassays on CEW (Helicoverpa zea)

Bioassays on CEW were conducted using a 128-well diet tray assay. One tofive second instar CEW larvae were placed in each well (3 mL) of thediet tray that had been previously filled with 1 mL of artificial dietto which 50 μg/cm² of the test compound (dissolved in 50 μL of 90:10acetone-water mixture) had been applied (to each of eight wells) andthen allowed to dry. Trays were covered with a clear self-adhesivecover, and held at 25° C., 14:10 light-dark for five to seven days.Percent mortality was recorded for the larvae in each well; activity inthe eight wells was then averaged. The results are indicated in thetable entitled “Table: Bio Results” (See Table Section).

Example 16 Bioassays on Green Peach Aphid (“GPA”) (Myzus persicae)

GPA is the most significant aphid pest of peach trees, causing decreasedgrowth, shriveling of the leaves, and the death of various tissues. Itis also hazardous because it acts as a vector for the transport of plantviruses, such as potato virus Y and potato leafroll virus to members ofthe nightshade/potato family Solanaceae, and various mosaic viruses tomany other food crops. GPA attacks such plants as broccoli, burdock,cabbage, carrot, cauliflower, daikon, eggplant, green beans, lettuce,macadamia, papaya, peppers, sweet potatoes, tomatoes, watercress, andzucchini, among other plants. GPA also attacks many ornamental cropssuch as carnation, chrysanthemum, flowering white cabbage, poinsettia,and roses. GPA has developed resistance to many pesticides.

Certain molecules disclosed in this document were tested against GPAusing procedures described in the following example. In the reporting ofthe results, the “GPA Rating Table” was used (See Table Section).

Cabbage seedlings grown in 3-inch pots, with 2-3 small (3-5 cm) trueleaves, were used as test substrate. The seedlings were infested with20-50 GPA (wingless adult and nymph stages) one day prior to chemicalapplication. Four pots with individual seedlings were used for eachtreatment. Test compounds (2 mg) were dissolved in 2 mL ofacetone/methanol (1:1) solvent, forming stock solutions of 1000 ppm testcompound. The stock solutions were diluted 5× with 0.025% Tween 20 inH₂O to obtain the solution at 200 ppm test compound. A hand-heldaspirator-type sprayer was used for spraying a solution to both sides ofcabbage leaves until runoff. Reference plants (solvent check) weresprayed with the diluent only containing 20% by volume ofacetone/methanol (1:1) solvent. Treated plants were held in a holdingroom for three days at approximately 25° C. and ambient relativehumidity (RH) prior to grading. Evaluation was conducted by counting thenumber of live aphids per plant under a microscope. Percent Control wasmeasured by using Abbott's correction formula (W. S. Abbott, “A Methodof Computing the Effectiveness of an Insecticide” J. Econ. Entomol. 18(1925), pp. 265-267) as follows.Corrected % Control=100*(X−Y)/X

-   -   where    -   X=No. of live aphids on solvent check plants and    -   Y=No. of live aphids on treated plants

The results are indicated in the table entitled “Table: Bio Results”(See Table Section).

Pesticidally Acceptable Acid Addition Salts, Salt Derivatives, Solvates,Ester Derivatives, Polymorphs, Isotopes and Radionuclides

Molecules of Formula One, Two, Three, and Four may be formulated intopesticidally acceptable acid addition salts. By way of a non-limitingexample, an amine function can form salts with hydrochloric,hydrobromic, sulfuric, phosphoric, acetic, benzoic, citric, malonic,salicylic, malic, fumaric, oxalic, succinic, tartaric, lactic, gluconic,ascorbic, maleic, aspartic, benzenesulfonic, methanesulfonic,ethanesulfonic, hydroxymethanesulfonic, and hydroxyethanesulfonic acids.Additionally, by way of a non-limiting example, an acid function canform salts including those derived from alkali or alkaline earth metalsand those derived from ammonia and amines. Examples of preferred cationsinclude sodium, potassium, and magnesium.

Molecules of Formula One, Two, Three, and Four may be formulated intosalt derivatives. By way of a non-limiting example, a salt derivativecan be prepared by contacting a free base with a sufficient amount ofthe desired acid to produce a salt. A free base may be regenerated bytreating the salt with a suitable dilute aqueous base solution such asdilute aqueous sodium hydroxide (NaOH), potassium carbonate, ammonia,and sodium bicarbonate. As an example, in many cases, a pesticide, suchas 2,4-D, is made more water-soluble by converting it to itsdimethylamine salt.

Molecules of Formula One, Two, Three, and Four may be formulated intostable complexes with a solvent, such that the complex remains intactafter the non-complexed solvent is removed. These complexes are oftenreferred to as “solvates.” However, it is particularly desirable to formstable hydrates with water as the solvent.

Molecules of Formula One, Two, Three, and Four may be made into esterderivatives. These ester derivatives can then be applied in the samemanner as the invention disclosed in this document is applied.

Molecules of Formula One, Two, Three, and Four may be made as variouscrystal polymorphs. Polymorphism is important in the development ofagrochemicals since different crystal polymorphs or structures of thesame molecule can have vastly different physical properties andbiological performances.

Molecules of Formula One, Two, Three, and Four may be made withdifferent isotopes. Of particular importance are molecules having ²H(also known as deuterium) in place of ¹H.

Molecules of Formula One, Two, Three, and Four may be made withdifferent radionuclides. Of particular importance are molecules having¹⁴C.

Stereoisomers

Molecules of Formula One, Two, Three, and Four may exist as one or morestereoisomers. Thus, certain molecules can be produced as racemicmixtures. It will be appreciated by those skilled in the art that onestereoisomer may be more active than the other stereoisomers. Individualstereoisomers may be obtained by known selective synthetic procedures,by conventional synthetic procedures using resolved starting materials,or by conventional resolution procedures.

Insecticides

Molecules of Formula One, Two, Three, and Four may also be used incombination (such as, in a compositional mixture, or a simultaneous orsequential application) with one or more of the followinginsecticides—1,2-dichloropropane, abamectin, acephate, acetamiprid,acethion, acetoprole, acrinathrin, acrylonitrile, alanycarb, aldicarb,aldoxycarb, aldrin, allethrin, allosamidin, allyxycarb,alpha-cypermethrin, alpha-ecdysone, alpha-endosulfan, amidithion,aminocarb, amiton, amiton oxalate, amitraz, anabasine, athidathion,azadirachtin, azamethiphos, azinphos-ethyl, azinphos-methyl, azothoate,barium hexafluorosilicate, barthrin, bendiocarb, benfuracarb, bensultap,beta-cyfluthrin, beta-cypermethrin, bifenthrin, bioallethrin,bioethanomethrin, biopermethrin, bistrifluoron, borax, boric acid,bromfenvinfos, bromocyclen, bromo-DDT, bromophos, bromophos-ethyl,bufencarb, buprofezin, butacarb, butathiofos, butocarboxim, butonate,butoxycarboxim, BYI-02960, cadusafos, calcium arsenate, calciumpolysulfide, camphechlor, carbanolate, carbaryl, carbofuran, carbondisulfide, carbon tetrachloride, carbophenothion, carbosulfan, cartap,cartap hydrochloride, chlorantraniliprole, chlorbicyclen, chlordane,chlordecone, chlordimeform, chlordimeform hydrochloride, chlorethoxyfos,chlorfenapyr, chlorfenvinphos, chlorfluazuron, chlormephos, chloroform,chloropicrin, chlorphoxim, chlorprazophos, chlorpyrifos,chlorpyrifos-methyl, chlorthiophos, chromafenozide, cinerin I, cinerinII, cinerins, cismethrin, cloethocarb, closantel, clothianidin, copperacetoarsenite, copper arsenate, copper naphthenate, copper oleate,coumaphos, coumithoate, crotamiton, crotoxyphos, crufomate, cryolite,cyanofenphos, cyanophos, cyanthoate, cyantraniliprole, cyclethrin,cycloprothrin, cyfluthrin, cyhalothrin, cypermethrin, cyphenothrin,cyromazine, cythioate, DDT, decarbofuran, deltamethrin, demephion,demephion-O, demephion-S, demeton, demeton-methyl, demeton-O,demeton-O-methyl, demeton-S, demeton-5-methyl, demeton-5-methylsulphon,diafenthiuron, dialifos, diatomaceous earth, diazinon, dicapthon,dichlofenthion, dichlorvos, dicresyl, dicrotophos, dicyclanil, dieldrin,diflubenzuron, dilor, dimefluthrin, dimefox, dimetan, dimethoate,dimethrin, dimethylvinphos, dimetilan, dinex, dinex-diclexine, dinoprop,dinosam, dinotefuran, diofenolan, dioxabenzolos, dioxacarb, dioxathion,disulfoton, dithicrofos, d-limonene, DNOC, DNOC-ammonium,DNOC-potassium, DNOC-sodium, doramectin, ecdysterone, emamectin,emamectin benzoate, EMPC, empenthrin, endosulfan, endothion, endrin,EPN, epofenonane, eprinomectin, esdepallethrine, esfenvalerate, etaphos,ethiofencarb, ethion, ethiprole, ethoate-methyl, ethoprophos, ethylformate, ethyl-DDD, ethylene dibromide, ethylene dichloride, ethyleneoxide, etofenprox, etrimfos, EXD, famphur, fenamiphos, fenazaflor,fenchlorphos, fenethacarb, fenfluthrin, fenitrothion, fenobucarb,fenoxacrim, fenoxycarb, fenpirithrin, fenpropathrin, fensulfothion,fenthion, fenthion-ethyl, fenvalerate, fipronil, flonicamid,flubendiamide (additionally resolved isomers thereof), flucofuron,flucycloxuron, flucythrinate, flufenerim, flufenoxuron, flufenprox,fluvalinate, fonofos, formetanate, formetanate hydrochloride,formothion, formparanate, formparanate hydrochloride, fosmethilan,fospirate, fosthietan, fufenozide, furathiocarb, furethrin,gamma-cyhalothrin, gamma-HCH, halfenprox, halofenozide, HCH, HEOD,heptachlor, heptenophos, heterophos, hexaflumuron, HHDN, hydramethylnon,hydrogen cyanide, hydroprene, hyquincarb, imidacloprid, imiprothrin,indoxacarb, iodomethane, IPSP, isazofos, isobenzan, isocarbophos,isodrin, isofenphos, isofenphos-methyl, isoprocarb, isoprothiolane,isothioate, isoxathion, ivermectin, jasmolin I, jasmolin II, jodfenphos,juvenile hormone I, juvenile hormone II, juvenile hormone III, kelevan,kinoprene, lambda-cyhalothrin, lead arsenate, lepimectin, leptophos,lindane, lirimfos, lufenuron, lythidathion, malathion, malonoben,mazidox, mecarbam, mecarphon, menazon, meperfluthrin, mephosfolan,mercurous chloride, mesulfenfos, metaflumizone, methacrifos,methamidophos, methidathion, methiocarb, methocrotophos, methomyl,methoprene, methothrin, methoxychlor, methoxyfenozide, methyl bromide,methyl isothiocyanate, methylchloroform, methylene chloride,metofluthrin, metolcarb, metoxadiazone, mevinphos, mexacarbate,milbemectin, milbemycin oxime, mipafox, mirex, molosultap,monocrotophos, monomehypo, monosultap, morphothion, moxidectin,naftalofos, naled, naphthalene, nicotine, nifluridide, nitenpyram,nithiazine, nitrilacarb, novaluron, noviflumuron, omethoate, oxamyl,oxydemeton-methyl, oxydeprofos, oxydisulfoton, para-dichlorobenzene,parathion, parathion-methyl, penfluoron, pentachlorophenol, permethrin,phenkapton, phenothrin, phenthoate, phorate, phosalone, phosfolan,phosmet, phosnichlor, phosphamidon, phosphine, phoxim, phoxim-methyl,pirimetaphos, pirimicarb, pirimiphos-ethyl, pirimiphos-methyl, potassiumarsenite, potassium thiocyanate, pp′-DDT, prallethrin, precocene I,precocene II, precocene III, primidophos, profenofos, profluralin,profluthrin, promacyl, promecarb, propaphos, propetamphos, propoxur,prothidathion, prothiofos, prothoate, protrifenbute, pymetrozine,pyraclofos, pyrafluprole, pyrazophos, pyresmethrin, pyrethrin I,pyrethrin II, pyrethrins, pyridaben, pyridalyl, pyridaphenthion,pyrifluquinazon, pyrimidifen, pyrimitate, pyriprole, pyriproxyfen,quassia, quinalphos, quinalphos-methyl, quinothion, rafoxanide,resmethrin, rotenone, ryania, sabadilla, schradan, selamectin,silafluofen, silica gel, sodium arsenite, sodium fluoride, sodiumhexafluorosilicate, sodium thiocyanate, sophamide, spinetoram, spinosad,spiromesifen, spirotetramat, sulcofuron, sulcofuron-sodium, sulfluramid,sulfotep, sulfoxaflor, sulfuryl fluoride, sulprofos, tau-fluvalinate,tazimcarb, TDE, tebufenozide, tebufenpyrad, tebupirimfos, teflubenzuron,tefluthrin, temephos, TEPP, terallethrin, terbufos, tetrachloroethane,tetrachlorvinphos, tetramethrin, tetramethylfluthrin,theta-cypermethrin, thiacloprid, thiamethoxam, thicrofos, thiocarboxime,thiocyclam, thiocyclam oxalate, thiodicarb, thiofanox, thiometon,thiosultap, thiosultap-disodium, thiosultap-monosodium, thuringiensin,tolfenpyrad, tralomethrin, transfluthrin, transpermethrin, triarathene,triazamate, triazophos, trichlorfon, trichlormetaphos-3, trichloronat,trifenofos, triflumuron, trimethacarb, triprene, vamidothion,vaniliprole, XMC, xylylcarb, zeta-cypermethrin, and zolaprofos(collectively these commonly named insecticides are defined as the“Insecticide Group”).

Acaricides

Molecules of Formula One, Two, Three, and Four may also be used incombination (such as, in a compositional mixture, or a simultaneous orsequential application) with one or more of the followingacaricides—acequinocyl, amidoflumet, arsenous oxide, azobenzene,azocyclotin, benomyl, benoxafos, benzoximate, benzyl benzoate,bifenazate, binapacryl, bromopropylate, chinomethionat, chlorbenside,chlorfenethol, chlorfenson, chlorfensulphide, chlorobenzilate,chloromebuform, chloromethiuron, chloropropylate, clofentezine,cyenopyrafen, cyflumetofen, cyhexatin, dichlofluanid, dicofol,dienochlor, diflovidazin, dinobuton, dinocap, dinocap-4, dinocap-6,dinocton, dinopenton, dinosulfon, dinoterbon, diphenyl sulfone,disulfuram, dofenapyn, etoxazole, fenazaquin, fenbutatin oxide,fenothiocarb, fenpyroximate, fenson, fentrifanil, fluacrypyrim,fluazuron, flubenzimine, fluenetil, flumethrin, fluorbenside,hexythiazox, mesulfen, MNAF, nikkomycins, proclonol, propargite,quintiofos, spirodiclofen, sulfuram, sulfur, tetradifon, tetranactin,tetrasul, and thioquinox (collectively these commonly named acaricidesare defined as the “Acaricide Group”).

Nematicides

Molecules of Formula One, Two, Three, and Four may also be used incombination (such as, in a compositional mixture, or a simultaneous orsequential application) with one or more of the followingnematicides—1,3-dichloropropene, benclothiaz, dazomet, dazomet-sodium,DBCP, DCIP, diamidafos, fluensulfone, fosthiazate, furfural, imicyafos,isamidofos, isazofos, metam, metam-ammonium, metam-potassium,metam-sodium, phosphocarb, and thionazin (collectively these commonlynamed nematicides are defined as the “Nematicide Group”)

Fungicides

Molecules of Formula One, Two, Three, and Four may also be used incombination (such as, in a compositional mixture, or a simultaneous orsequential application) with one or more of the followingfungicides—(3-ethoxypropyl)mercury bromide, 2-methoxyethylmercurychloride, 2-phenylphenol, 8-hydroxyquinoline sulfate,8-phenylmercurioxyquinoline, acibenzolar, acibenzolar-5-methyl,acypetacs, acypetacs-copper, acypetacs-zinc, aldimorph, allyl alcohol,ametoctradin, amisulbrom, ampropylfos, anilazine, aureofungin,azaconazole, azithiram, azoxystrobin, barium polysulfide, benalaxyl,benalaxyl-M, benodanil, benomyl, benquinox, bentaluron, benthiavalicarb,benthiavalicarb-isopropyl, benzalkonium chloride, benzamacril,benzamacril-isobutyl, benzamorf, benzohydroxamic acid, bethoxazin,binapacryl, biphenyl, bitertanol, bithionol, bixafen, blasticidin-S,Bordeaux mixture, boscalid, bromuconazole, bupirimate, Burgundy mixture,buthiobate, butylamine, calcium polysulfide, captafol, captan,carbamorph, carbendazim, carboxin, carpropamid, carvone, Cheshuntmixture, chinomethionat, chlobenthiazone, chloraniformethan, chloranil,chlorfenazole, chlorodinitronaphthalene, chloroneb, chloropicrin,chlorothalonil, chlorquinox, chlozolinate, climbazole, clotrimazole,copper acetate, copper carbonate, basic, copper hydroxide, coppernaphthenate, copper oleate, copper oxychloride, copper silicate, coppersulfate, copper zinc chromate, cresol, cufraneb, cuprobam, cuprousoxide, cyazofamid, cyclafuramid, cycloheximide, cyflufenamid, cymoxanil,cypendazole, cyproconazole, cyprodinil, dazomet, dazomet-sodium, DB CP,debacarb, decafentin, dehydroacetic acid, dichlofluanid, dichlone,dichlorophen, dichlozoline, diclobutrazol, diclocymet, diclomezine,diclomezine-sodium, dicloran, diethofencarb, diethyl pyrocarbonate,difenoconazole, diflumetorim, dimethirimol, dimethomorph, dimoxystrobin,diniconazole, diniconazole-M, dinobuton, dinocap, dinocap-4, dinocap-6,dinocton, dinopenton, dinosulfon, dinoterbon, diphenylamine,dipyrithione, disulfuram, ditalimfos, dithianon, DNOC, DNOC-ammonium,DNOC-potassium, DNOC-sodium, dodemorph, dodemorph acetate, dodemorphbenzoate, dodicin, dodicin-sodium, dodine, drazoxolon, edifenphos,epoxiconazole, etaconazole, etem, ethaboxam, ethirimol, ethoxyquin,ethylmercury 2,3-dihydroxypropyl mercaptide, ethylmercury acetate,ethylmercury bromide, ethylmercury chloride, ethylmercury phosphate,etridiazole, famoxadone, fenamidone, fenaminosulf, fenapanil, fenarimol,fenbuconazole, fenfuram, fenhexamid, fenitropan, fenoxanil, fenpiclonil,fenpropidin, fenpropimorph, fentin, fentin chloride, fentin hydroxide,ferbam, ferimzone, fluazinam, fludioxonil, flumetover, flumorph,fluopicolide, fluopyram, fluoroimide, fluotrimazole, fluoxastrobin,fluquinconazole, flusilazole, flusulfamide, flutianil, flutolanil,flutriafol, fluxapyroxad, folpet, formaldehyde, fosetyl,fosetyl-aluminium, fuberidazole, furalaxyl, furametpyr, furcarbanil,furconazole, furconazole-cis, furfural, furmecyclox, furophanate,glyodin, griseofulvin, guazatine, halacrinate, hexachlorobenzene,hexachlorobutadiene, hexaconazole, hexylthiofos, hydrargaphen,hymexazol, imazalil, imazalil nitrate, imazalil sulfate, imibenconazole,iminoctadine, iminoctadine triacetate, iminoctadine trialbesilate,iodomethane, ipconazole, iprobenfos, iprodione, iprovalicarb,isoprothiolane, isopyrazam, isotianil, isovaledione, kasugamycin,kresoxim-methyl, mancopper, mancozeb, mandipropamid, maneb, mebenil,mecarbinzid, mepanipyrim, mepronil, meptyldinocap, mercuric chloride,mercuric oxide, mercurous chloride, metalaxyl, metalaxyl-M, metam,metam-ammonium, metam-potassium, metam-sodium, metazoxolon, metconazole,methasulfocarb, methfuroxam, methyl bromide, methyl isothiocyanate,methylmercury benzoate, methylmercury dicyandiamide, methylmercurypentachlorophenoxide, metiram, metominostrobin, metrafenone,metsulfovax, milneb, myclobutanil, myclozolin,N-(ethylmercury)-p-toluenesulphonanilide, nabam, natamycin,nitrostyrene, nitrothal-isopropyl, nuarimol, OCH, octhilinone, ofurace,orysastrobin, oxadixyl, oxine-copper, oxpoconazole, oxpoconazolefumarate, oxycarboxin, pefurazoate, penconazole, pencycuron, penflufen,pentachlorophenol, penthiopyrad, phenylmercuriurea, phenylmercuryacetate, phenylmercury chloride, phenylmercury derivative ofpyrocatechol, phenylmercury nitrate, phenylmercury salicylate,phosdiphen, phthalide, picoxystrobin, piperalin, polycarbamate,polyoxins, polyoxorim, polyoxorim-zinc, potassium azide, potassiumpolysulfide, potassium thiocyanate, probenazole, prochloraz,procymidone, propamocarb, propamocarb hydrochloride, propiconazole,propineb, proquinazid, prothiocarb, prothiocarb hydrochloride,prothioconazole, pyracarbolid, pyraclostrobin, pyraclostrobin,pyrametostrobin, pyraoxystrobin, pyrazophos, pyribencarb, pyridinitril,pyrifenox, pyrimethanil, pyriofenone, pyroquilon, pyroxychlor,pyroxyfur, quinacetol, quinacetol sulfate, quinazamid, quinconazole,quinoxyfen, quintozene, rabenzazole, salicylanilide, sedaxane,silthiofam, simeconazole, sodium azide, sodium orthophenylphenoxide,sodium pentachlorophenoxide, sodium polysulfide, spiroxamine,streptomycin, sulfur, sultropen, TCMTB, tebuconazole, tebufloquin,tecloftalam, tecnazene, tecoram, tetraconazole, thiabendazole,thiadifluor, thicyofen, thifluzamide, thiochlorfenphim, thiomersal,thiophanate, thiophanate-methyl, thioquinox, thiram, tiadinil, tioxymid,tolclofos-methyl, tolylfluanid, tolylmercury acetate, triadimefon,triadimenol, triamiphos, triarimol, triazbutil, triazoxide, tributyltinoxide, trichlamide, tricyclazole, tridemorph, trifloxystrobin,triflumizole, triforine, triticonazole, uniconazole, uniconazole-P,validamycin, valifenalate, vinclozolin, zarilamid, zinc naphthenate,zineb, ziram, zoxamide (collectively these commonly named fungicides aredefined as the “Fungicide Group”).

Herbicides

Molecules of Formula One, Two, Three, and Four may also be used incombination (such as, in a compositional mixture, or a simultaneous orsequential application) with one or more of the followingherbicides—2,3,6-TBA, 2,3,6-TBA-dimethylammonium, 2,3,6-TBA-sodium,2,4,5-T, 2,4,5-T-2-butoxypropyl, 2,4,5-T-2-ethylhexyl,2,4,5-T-3-butoxypropyl, 2,4,5-TB, 2,4,5-T-butomethyl, 2,4,5-T-butotyl,2,4,5-T-butyl, 2,4,5-T-isobutyl, 2,4,5-T-isoctyl, 2,4,5-T-isopropyl,2,4,5-T-methyl, 2,4,5-T-pentyl, 2,4,5-T-sodium,2,4,5-T-triethylammonium, 2,4,5-T-trolamine, 2,4-D,2,4-D-2-butoxypropyl, 2,4-D-2-ethylhexyl, 2,4-D-3-butoxypropyl,2,4-D-ammonium, 2,4-DB, 2,4-DB-butyl, 2,4-DB-dimethylammonium,2,4-DB-isoctyl, 2,4-DB-potassium, 2,4-DB-sodium, 2,4-D-butotyl,2,4-D-butyl, 2,4-D-diethylammonium, 2,4-D-dimethylammonium,2,4-D-diolamine, 2,4-D-dodecylammonium, 2,4-DEB, 2,4-DEP, 2,4-D-ethyl,2,4-D-heptylammonium, 2,4-D-isobutyl, 2,4-D-isoctyl, 2,4-D-isopropyl,2,4-D-isopropylammonium, 2,4-D-lithium, 2,4-D-meptyl, 2,4-D-methyl,2,4-D-octyl, 2,4-D-pentyl, 2,4-D-potassium, 2,4-D-propyl, 2,4-D-sodium,2,4-D-tefuryl, 2,4-D-tetradecylammonium, 2,4-D-triethylammonium,2,4-D-tris(2-hydroxypropyl)ammonium, 2,4-D-trolamine, 3,4-DA, 3,4-DB,3,4-DP, 4-CPA, 4-CPB, 4-CPP, acetochlor, acifluorfen,acifluorfen-methyl, acifluorfen-sodium, aclonifen, acrolein, alachlor,allidochlor, alloxydim, alloxydim-sodium, allyl alcohol, alorac,ametridione, ametryn, amibuzin, amicarbazone, amidosulfuron,aminocyclopyrachlor, aminocyclopyrachlor-methyl,aminocyclopyrachlor-potassium, aminopyralid, aminopyralid-potassium,aminopyralid-tris(2-hydroxypropyl)ammonium, amiprofos-methyl, amitrole,ammonium sulfamate, anilofos, anisuron, asulam, asulam-potassium,asulam-sodium, atraton, atrazine, azafenidin, azimsulfuron, aziprotryne,barban, B CPC, beflubutamid, benazolin, benazolin-dimethylammonium,benazolin-ethyl, benazolin-potassium, bencarbazone, benfluralin,benfuresate, bensulfuron, bensulfuron-methyl, bensulide, bentazone,bentazone-sodium, benzadox, benzadox-ammonium, benzfendizone, benzipram,benzobicyclon, benzofenap, benzofluor, benzoylprop, benzoylprop-ethyl,benzthiazuron, bicyclopyrone, bifenox, bilanafos, bilanafos-sodium,bispyribac, bispyribac-sodium, borax, bromacil, bromacil-lithium,bromacil-sodium, bromobonil, bromobutide, bromofenoxim, bromoxynil,bromoxynil butyrate, bromoxynil heptanoate, bromoxynil octanoate,bromoxynil-potassium, brompyrazon, butachlor, butafenacil, butamifos,butenachlor, buthidazole, buthiuron, butralin, butroxydim, buturon,butylate, cacodylic acid, cafenstrole, calcium chlorate, calciumcyanamide, cambendichlor, carbasulam, carbetamide, carboxazole,carfentrazone, carfentrazone-ethyl, CDEA, CEPC, chlomethoxyfen,chloramben, chloramben-ammonium, chloramben-diolamine,chloramben-methyl, chloramben-methylammonium, chloramben-sodium,chloranocryl, chlorazifop, chlorazifop-propargyl, chlorazine,chlorbromuron, chlorbufam, chloreturon, chlorfenac, chlorfenac-sodium,chlorfenprop, chlorfenprop-methyl, chlorflurazole, chlorflurenol,chlorflurenol-methyl, chloridazon, chlorimuron, chlorimuron-ethyl,chlomitrofen, chloropon, chlorotoluron, chloroxuron, chloroxynil,chlorprocarb, chlorpropham, chlorsulfuron, chlorthal,chlorthal-dimethyl, chlorthal-monomethyl, chlorthiamid, cinidon-ethyl,cinmethylin, cinosulfuron, cisanilide, clethodim, cliodinate,clodinafop, clodinafop-propargyl, clofop, clofop-isobutyl, clomazone,clomeprop, cloprop, cloproxydim, clopyralid, clopyralid-methyl,clopyralid-olamine, clopyralid-potassium,clopyralid-tris(2-hydroxypropyl)ammonium, cloransulam,cloransulam-methyl, CMA, copper sulfate, CPMF, CPPC, credazine, cresol,cumyluron, cyanamide, cyanatryn, cyanazine, cycloate, cyclosulfamuron,cycloxydim, cycluron, cyhalofop, cyhalofop-butyl, cyperquat, cyperquatchloride, cyprazine, cyprazole, cypromid, daimuron, dalapon,dalapon-calcium, dalapon-magnesium, dalapon-sodium, dazomet,dazomet-sodium, delachlor, desmedipham, desmetryn, di-allate, dicamba,dicamba-dimethylammonium, dicamba-diolamine, dicamba-isopropylammonium,dicamba-methyl, dicamba-olamine, dicamba-potassium, dicamba-sodium,dicamba-trolamine, dichlobenil, dichloralurea, dichlormate, dichlorprop,dichlorprop-2-ethylhexyl, dichlorprop-butotyl,dichlorprop-dimethylammonium, dichlorprop-ethylammonium,dichlorprop-isoctyl, dichlorprop-methyl, dichlorprop-P,dichlorprop-P-dimethylammonium, dichlorprop-potassium,dichlorprop-sodium, diclofop, diclofop-methyl, diclosulam, diethamquat,diethamquat dichloride, diethatyl, diethatyl-ethyl, difenopenten,difenopenten-ethyl, difenoxuron, difenzoquat, difenzoquat metilsulfate,diflufenican, diflufenzopyr, diflufenzopyr-sodium, dimefuron,dimepiperate, dimethachlor, dimethametryn, dimethenamid, dimethenamid-P,dimexano, dimidazon, dinitramine, dinofenate, dinoprop, dinosam,dinoseb, dinoseb acetate, dinoseb-ammonium, dinoseb-diolamine,dinoseb-sodium, dinoseb-trolamine, dinoterb, dinoterb acetate,diphacinone-sodium, diphenamid, dipropetryn, diquat, diquat dibromide,disul, disul-sodium, dithiopyr, diuron, DMPA, DNOC, DNOC-ammonium,DNOC-potassium, DNOC-sodium, DSMA, EBEP, eglinazine, eglinazine-ethyl,endothal, endothal-diammonium, endothal-dipotassium, endothal-disodium,epronaz, EPTC, erbon, esprocarb, ethalfluralin, ethametsulfuron,ethametsulfuron-methyl, ethidimuron, ethiolate, ethofumesate, ethoxyfen,ethoxyfen-ethyl, ethoxysulfuron, etinofen, etnipromid, etobenzanid, EXD,fenasulam, fenoprop, fenoprop-3-butoxypropyl, fenoprop-butomethyl,fenoprop-butotyl, fenoprop-butyl, fenoprop-isoctyl, fenoprop-methyl,fenoprop-potassium, fenoxaprop, fenoxaprop-ethyl, fenoxaprop-P,fenoxaprop-P-ethyl, fenoxasulfone, fenteracol, fenthiaprop,fenthiaprop-ethyl, fentrazamide, fenuron, fenuron TCA, ferrous sulfate,flamprop, flamprop-isopropyl, flamprop-M, flamprop-methyl,flamprop-M-isopropyl, flamprop-M-methyl, flazasulfuron, florasulam,fluazifop, fluazifop-butyl, fluazifop-methyl, fluazifop-P,fluazifop-P-butyl, fluazolate, flucarbazone, flucarbazone-sodium,flucetosulfuron, fluchloralin, flufenacet, flufenican, flufenpyr,flufenpyr-ethyl, flumetsulam, flumezin, flumiclorac, flumiclorac-pentyl,flumioxazin, flumipropyn, fluometuron, fluorodifen, fluoroglycofen,fluoroglycofen-ethyl, fluoromidine, fluoronitrofen, fluothiuron,flupoxam, flupropacil, flupropanate, flupropanate-sodium,flupyrsulfuron, flupyrsulfuron-methyl-sodium, fluridone,fluorochloridone, fluoroxypyr, fluoroxypyr-butomethyl,fluoroxypyr-meptyl, flurtamone, fluthiacet, fluthiacet-methyl,fomesafen, fomesafen-sodium, foramsulfuron, fosamine, fosamine-ammonium,furyloxyfen, glufosinate, glufosinate-ammonium, glufosinate-P,glufosinate-P-ammonium, glufosinate-P-sodium, glyphosate,glyphosate-diammonium, glyphosate-dimethylammonium,glyphosate-isopropylammonium, glyphosate-monoammonium,glyphosate-potassium, glyphosate-sesquisodium, glyphosate-trimesium,halosafen, halosulfuron, halosulfuron-methyl, haloxydine, haloxyfop,haloxyfop-etotyl, haloxyfop-methyl, haloxyfop-P, haloxyfop-P-etotyl,haloxyfop-P-methyl, haloxyfop-sodium, hexachloroacetone, hexaflurate,hexazinone, imazamethabenz, imazamethabenz-methyl, imazamox,imazamox-ammonium, imazapic, imazapic-ammonium, imazapyr,imazapyr-isopropylammonium, imazaquin, imazaquin-ammonium,imazaquin-methyl, imazaquin-sodium, imazethapyr, imazethapyr-ammonium,imazosulfuron, indanofan, indaziflam, iodobonil, iodomethane,iodosulfuron, iodosulfuron-methyl-sodium, ioxynil, ioxynil octanoate,ioxynil-lithium, ioxynil-sodium, ipazine, ipfencarbazone, iprymidam,isocarbamid, isocil, isomethiozin, isonoruron, isopolinate, isopropalin,isoproturon, isouron, isoxaben, isoxachlortole, isoxaflutole,isoxapyrifop, karbutilate, ketospiradox, lactofen, lenacil, linuron,MAA, MAMA, MCPA, MCPA-2-ethylhexyl, MCPA-butotyl, MCPA-butyl,MCPA-dimethylammonium, MCPA-diolamine, MCPA-ethyl, MCPA-isobutyl,MCPA-isoctyl, MCPA-isopropyl, MCPA-methyl, MCPA-olamine, MCPA-potassium,MCPA-sodium, MCPA-thioethyl, MCPA-trolamine, MCPB, MCPB-ethyl,MCPB-methyl, MCPB-sodium, mecoprop, mecoprop-2-ethylhexyl,mecoprop-dimethylammonium, mecoprop-diolamine, mecoprop-ethadyl,mecoprop-isoctyl, mecoprop-methyl, mecoprop-P,mecoprop-P-dimethylammonium, mecoprop-P-isobutyl, mecoprop-potassium,mecoprop-P-potassium, mecoprop-sodium, mecoprop-trolamine, medinoterb,medinoterb acetate, mefenacet, mefluidide, mefluidide-diolamine,mefluidide-potassium, mesoprazine, mesosulfuron, mesosulfuron-methyl,mesotrione, metam, metam-ammonium, metamifop, metamitron,metam-potassium, metam-sodium, metazachlor, metazosulfuron, metflurazon,methabenzthiazuron, methalpropalin, methazole, methiobencarb,methiozolin, methiuron, methometon, methoprotryne, methyl bromide,methyl isothiocyanate, methyldymron, metobenzuron, metolachlor,metosulam, metoxuron, metribuzin, metsulfuron, metsulfuron-methyl,molinate, monalide, monisouron, monochloroacetic acid, monolinuron,monuron, monuron TCA, morfamquat, morfamquat dichloride, MSMA,naproanilide, napropamide, naptalam, naptalam-sodium, neburon,nicosulfuron, nipyraclofen, nitralin, nitrofen, nitrofluorfen,norflurazon, noruron, OCH, orbencarb, ortho-dichlorobenzene,orthosulfamuron, oryzalin, oxadiargyl, oxadiazon, oxapyrazon,oxapyrazon-dimolamine, oxapyrazon-sodium, oxasulfuron, oxaziclomefone,oxyfluorfen, parafluoron, paraquat, paraquat dichloride, paraquatdimetilsulfate, pebulate, pelargonic acid, pendimethalin, penoxsulam,pentachlorophenol, pentanochlor, pentoxazone, perfluidone, pethoxamid,phenisopham, phenmedipham, phenmedipham-ethyl, phenobenzuron,phenylmercury acetate, picloram, picloram-2-ethylhexyl,picloram-isoctyl, picloram-methyl, picloram-olamine, picloram-potassium,picloram-triethylammonium, picloram-tris(2-hydroxypropyl)ammonium,picolinafen, pinoxaden, piperophos, potassium arsenite, potassium azide,potassium cyanate, pretilachlor, primisulfuron, primisulfuron-methyl,procyazine, prodiamine, profluazol, profluralin, profoxydim,proglinazine, proglinazine-ethyl, prometon, prometryn, propachlor,propanil, propaquizafop, propazine, propham, propisochlor,propoxycarbazone, propoxycarbazone-sodium, propyrisulfuron, propyzamide,prosulfalin, prosulfocarb, prosulfuron, proxan, proxan-sodium,prynachlor, pydanon, pyraclonil, pyraflufen, pyraflufen-ethyl,pyrasulfotole, pyrazolynate, pyrazosulfuron, pyrazosulfuron-ethyl,pyrazoxyfen, pyribenzoxim, pyributicarb, pyriclor, pyridafol, pyridate,pyriftalid, pyriminobac, pyriminobac-methyl, pyrimisulfan, pyrithiobac,pyrithiobac-sodium, pyroxasulfone, pyroxsulam, quinclorac, quinmerac,quinoclamine, quinonamid, quizalofop, quizalofop-ethyl, quizalofop-P,quizalofop-P-ethyl, quizalofop-P-tefuryl, rhodethanil, rimsulfuron,saflufenacil, sebuthylazine, secbumeton, sethoxydim, siduron, simazine,simeton, simetryn, SMA, S-metolachlor, sodium arsenite, sodium azide,sodium chlorate, sulcotrione, sulfallate, sulfentrazone, sulfometuron,sulfometuron-methyl, sulfosulfuron, sulfuric acid, sulglycapin, swep,TCA, TCA-ammonium, TCA-calcium, TCA-ethadyl, TCA-magnesium, TCA-sodium,tebutam, tebuthiuron, tefuryltrione, tembotrione, tepraloxydim,terbacil, terbucarb, terbuchlor, terbumeton, terbuthylazine, terbutryn,tetrafluoron, thenylchlor, thiazafluoron, thiazopyr, thidiazimin,thidiazuron, thiencarbazone, thiencarbazone-methyl, thifensulfuron,thifensulfuron-methyl, thiobencarb, tiocarbazil, tioclorim, topramezone,tralkoxydim, tri-allate, triasulfuron, triaziflam, tribenuron,tribenuron-methyl, tricamba, triclopyr, triclopyr-butotyl,triclopyr-ethyl, triclopyr-triethylammonium, tridiphane, trietazine,trifloxysulfuron, trifloxysulfuron-sodium, trifluralin, triflusulfuron,triflusulfuron-methyl, trifop, trifop-methyl, trifopsime,trihydroxytriazine, trimeturon, tripropindan, tritac, tritosulfuron,vernolate, xylachlor, (collectively these commonly named herbicides aredefined as the “Herbicide Group”).

Biopesticides

Molecules of Formula One, Two, Three, and Four may also be used incombination (such as in a compositional mixture, or a simultaneous orsequential application) with one or more biopesticides. The term“biopesticide” is used for microbial biological pest control agents thatare applied in a similar manner to chemical pesticides. Commonly theseare bacterial, but there are also examples of fungal control agents,including Trichoderma spp. and Ampelomyces quisqualis (a control agentfor grape powdery mildew). Bacillus subtilis are used to control plantpathogens. Weeds and rodents have also been controlled with microbialagents. One well-known insecticide example is Bacillus thuringiensis, abacterial disease of Lepidoptera, Coleoptera, and Diptera. Because ithas little effect on other organisms, it is considered moreenvironmentally friendly than synthetic pesticides. Biologicalinsecticides include products based on:

1. entomopathogenic fungi (e.g. Metarhizium anisopliae);

2. entomopathogenic nematodes (e.g. Steinemema feltiae); and

3. entomopathogenic viruses (e.g. Cydia pomonella granulovirus).

Other examples of entomopathogenic organisms include, but are notlimited to, baculoviruses, bacteria and other prokaryotic organisms,fungi, protozoa and Microsproridia. Biologically derived insecticidesinclude, but not limited to, rotenone, veratridine, as well as microbialtoxins; insect tolerant or resistant plant varieties; and organismsmodified by recombinant DNA technology to either produce insecticides orto convey an insect resistant property to the genetically modifiedorganism. In one embodiment, the molecules of Formula One, Two, Three,and Four may be used with one or more biopesticides in the area of seedtreatments and soil amendments. The Manual of Biocontrol Agents gives areview of the available biological insecticide (and other biology-basedcontrol) products. Copping L. G. (ed.) (2004). The Manual of BiocontrolAgents (formerly the Biopesticide Manual) 3rd Edition. British CropProduction Council (BCPC), Farnham, Surrey UK.

Other Active Compounds

Molecules of Formula One, Two, Three, and Four may also be used incombination (such as in a compositional mixture, or a simultaneous orsequential application) with one or more of the following:

-   1.    3-(4-chloro-2,6-dimethylphenyl)-4-hydroxy-8-oxa-1-azaspiro[4,5]dec-3-en-2-one;-   2.    3-(4′-chloro-2,4-dimethyl[1,1′-biphenyl]-3-yl)-4-hydroxy-8-oxa-1-azaspiro[4,5]dec-3-en-2-one;-   3. 4-[[(6-chloro-3-pyridinyl)methyl]methylamino]-2(5H)-furanone;-   4.    4-[[(6-chloro-3-pyridinyl)methyl]cyclopropylamino]-2(5H)-furanone;-   5.    3-chloro-N2-[(1S)-1-methyl-2-(methylsulfonyl)ethyl]-N1-[2-methyl-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]-1,2-benzenedicarboxamide;-   6. 2-cyano-N-ethyl-4-fluoro-3-methoxy-benenesulfonamide;-   7. 2-cyano-N-ethyl-3-methoxy-benzenesulfonamide;-   8. 2-cyano-3-difluoromethoxy-N-ethyl-4-fluoro-benzenesulfonamide;-   9. 2-cyano-3-fluoromethoxy-N-ethyl-benzenesulfonamide;-   10. 2-cyano-6-fluoro-3-methoxy-N,N-dimethyl-benzenesulfonamide;-   11. 2-cyano-N-ethyl-6-fluoro-3-methoxy-N-methyl-benzenesulfonamide;-   12. 2-cyano-3-difluoromethoxy-N,N-dimethylbenzenesulfon-amide;-   13.    3-(difluoromethyl)-N-[2-(3,3-dimethylbutyl)phenyl]-1-methyl-1H-pyrazole-4-carboxamide;-   14.    N-ethyl-2,2-dimethylpropionamide-2-(2,6-dichloro-α,α,α-trifluoro-p-tolyl)hydrazone;-   15.    N-ethyl-2,2-dichloro-1-methylcyclopropane-carboxamide-2-(2,6-dichloro-α,α,α-trifluoro-p-tolyl)hydrazone    nicotine;-   16.    O-{(E-)-[2-(4-chloro-phenyl)-2-cyano-1-(2-trifluoromethylphenyl)-vinyl]}S-methyl    thiocarbonate;-   17.    (E)-N1-[2-chloro-1,3-thiazol-5-ylmethyl)]-N2-cyano-N1-methylacetamidine;-   18.    1-(6-chloropyridin-3-ylmethyl)-7-methyl-8-nitro-1,2,3,5,6,7-hexahydro-imidazo[1,2-a]pyridin-5-ol;-   19. 4-[4-chlorophenyl-(2-butylidine-hydrazono)methyl)]phenyl    mesylate; and-   20.    N-Ethyl-2,2-dichloro-1-methylcyclopropanecarboxamide-2-(2,6-dichloro-alpha,alpha,alpha-trifluoro-p-tolyl)hydrazone.

Molecules of Formula One, Two, Three, and Four may also be used incombination (such as in a compositional mixture, or a simultaneous orsequential application) with one or more compounds in the followinggroups: algicides, antifeedants, avicides, bactericides, birdrepellents, chemosterilants, herbicide safeners, insect attractants,insect repellents, mammal repellents, mating disrupters, molluscicides,plant activators, plant growth regulators, rodenticides, and/orvirucides (collectively these commonly named groups are defined as the“AI Group”). It should be noted that compounds falling within the AIGroup, Insecticide Group, Fungicide Group, Herbicide Group, AcaricideGroup, or Nematicide Group might be in more than one group, because ofmultiple activities the compound has. For more information consult the“COMPENDIUM OF PESTICIDE COMMON NAMES” located athttp://www.alanwood.net/pesticides/indexhtml. Also consult “THEPESTICIDE MANUAL” 14th Edition, edited by C D S Tomlin, copyright 2006by British Crop Production Council, or its prior or more recenteditions.

Synergistic Mixtures and Synergists

Molecules of Formula One, Two, Three, and Four may be used with thecompounds in the Insecticide Group to form synergistic mixtures wherethe mode of action of such compounds compared to the mode of action ofthe molecules of Formula One, Two, Three, and Four are the same,similar, or different. Examples of modes of action include, but are notlimited to: acetylcholinesterase inhibitor; sodium channel modulator;chitin biosynthesis inhibitor; GABA-gated chloride channel antagonist;GABA and glutamate-gated chloride channel agonist; acetylcholinereceptor agonist; MET I inhibitor; Mg-stimulated ATPase inhibitor;nicotinic acetylcholine receptor; Midgut membrane disrupter; oxidativephosphorylation disrupter, and ryanodine receptor (RyRs). Additionally,molecules of Formula One, Two, Three, and Four may be used withcompounds in the Fungicide Group, Acaricide Group, Herbicide Group, orNematicide Group to form synergistic mixtures. Furthermore, molecules ofFormula One, Two, Three, and Four may be used with other activecompounds, such as the compounds under the heading “OTHER ACTIVECOMPOUNDS”, algicides, avicides, bactericides, molluscicides,rodenticides, virucides, herbicide safeners, adjuvants, and/orsurfactants to form synergistic mixtures. Generally, weight ratios ofthe molecules of Formula One, Two, Three, and Four in a synergisticmixture with another compound are from about 10:1 to about 1:10,preferably from about 5:1 to about 1:5, and more preferably from about3:1, and even more preferably about 1:1. Additionally, the followingcompounds are known as synergists and may be used with the moleculesdisclosed in Formula One: piperonyl butoxide, piprotal, propyl isome,sesamex, sesamolin, sulfoxide, and tribufos (collectively thesesynergists are defined as the “Synergists Group”).

Formulations

A pesticide is rarely suitable for application in its pure form. It isusually necessary to add other substances so that the pesticide can beused at the required concentration and in an appropriate form,permitting ease of application, handling, transportation, storage, andmaximum pesticide activity. Thus, pesticides are formulated into, forexample, baits, concentrated emulsions, dusts, emulsifiableconcentrates, fumigants, gels, granules, microencapsulations, seedtreatments, suspension concentrates, suspoemulsions, tablets, watersoluble liquids, water dispersible granules or dry flowables, wettablepowders, and ultra low volume solutions. For further information onformulation types see “Catalogue of Pesticide Formulation Types andInternational Coding System” Technical Monograph n^(o)2, 5th Edition byCropLife International (2002).

Pesticides are applied most often as aqueous suspensions or emulsionsprepared from concentrated formulations of such pesticides. Suchwater-soluble, water-suspendable, or emulsifiable formulations areeither solids, usually known as wettable powders, or water dispersiblegranules, or liquids usually known as emulsifiable concentrates, oraqueous suspensions. Wettable powders, which may be compacted to formwater dispersible granules, comprise an intimate mixture of thepesticide, a carrier, and surfactants. The concentration of thepesticide is usually from about 10% to about 90% by weight. The carrieris usually chosen from among the attapulgite clays, the montmorilloniteclays, the diatomaceous earths, or the purified silicates. Effectivesurfactants, comprising from about 0.5% to about 10% of the wettablepowder, are found among sulfonated lignins, condensednaphthalenesulfonates, naphthalenesulfonates, alkylbenzenesulfonates,alkyl sulfates, and non-ionic surfactants such as ethylene oxide adductsof alkyl phenols.

Emulsifiable concentrates of pesticides comprise a convenientconcentration of a pesticide, such as from about 50 to about 500 gramsper liter of liquid dissolved in a carrier that is either a watermiscible solvent or a mixture of water-immiscible organic solvent andemulsifiers. Useful organic solvents include aromatics, especiallyxylenes and petroleum fractions, especially the high-boilingnaphthalenic and olefinic portions of petroleum such as heavy aromaticnaphtha. Other organic solvents may also be used, such as the terpenicsolvents including rosin derivatives, aliphatic ketones such ascyclohexanone, and complex alcohols such as 2-ethoxyethanol. Suitableemulsifiers for emulsifiable concentrates are chosen from conventionalanionic and non-ionic surfactants.

Aqueous suspensions comprise suspensions of water-insoluble pesticidesdispersed in an aqueous carrier at a concentration in the range fromabout 5% to about 50% by weight. Suspensions are prepared by finelygrinding the pesticide and vigorously mixing it into a carrier comprisedof water and surfactants. Ingredients, such as inorganic salts andsynthetic or natural gums may also be added, to increase the density andviscosity of the aqueous carrier. It is often most effective to grindand mix the pesticide at the same time by preparing the aqueous mixtureand homogenizing it in an implement such as a sand mill, ball mill, orpiston-type homogenizer.

Pesticides may also be applied as granular compositions that areparticularly useful for applications to the soil. Granular compositionsusually contain from about 0.5% to about 10% by weight of the pesticide,dispersed in a carrier that comprises clay or a similar substance. Suchcompositions are usually prepared by dissolving the pesticide in asuitable solvent and applying it to a granular carrier which has beenpre-formed to the appropriate particle size, in the range of from about0.5 to about 3 mm. Such compositions may also be formulated by making adough or paste of the carrier and compound and crushing and drying toobtain the desired granular particle size.

Dusts containing a pesticide are prepared by intimately mixing thepesticide in powdered form with a suitable dusty agricultural carrier,such as kaolin clay, ground volcanic rock, and the like. Dusts cansuitably contain from about 1% to about 10% of the pesticide. They canbe applied as a seed dressing or as a foliage application with a dustblower machine.

It is equally practical to apply a pesticide in the form of a solutionin an appropriate organic solvent, usually petroleum oil, such as thespray oils, which are widely used in agricultural chemistry.

Pesticides can also be applied in the form of an aerosol composition. Insuch compositions the pesticide is dissolved or dispersed in a carrier,which is a pressure-generating propellant mixture. The aerosolcomposition is packaged in a container from which the mixture isdispensed through an atomizing valve.

Pesticide baits are formed when the pesticide is mixed with food or anattractant or both. When the pests eat the bait they also consume thepesticide. Baits may take the form of granules, gels, flowable powders,liquids, or solids. They can be used in pest harborages.

Fumigants are pesticides that have a relatively high vapor pressure andhence can exist as a gas in sufficient concentrations to kill pests insoil or enclosed spaces. The toxicity of the fumigant is proportional toits concentration and the exposure time. They are characterized by agood capacity for diffusion and act by penetrating the pest'srespiratory system or being absorbed through the pest's cuticle.Fumigants are applied to control stored product pests under gas proofsheets, in gas sealed rooms or buildings or in special chambers.

Pesticides can be microencapsulated by suspending the pesticideparticles or droplets in plastic polymers of various types. By alteringthe chemistry of the polymer or by changing factors in the processing,microcapsules can be formed of various sizes, solubility, wallthicknesses, and degrees of penetrability. These factors govern thespeed with which the active ingredient within is released, which inturn, affects the residual performance, speed of action, and odor of theproduct.

Oil solution concentrates are made by dissolving pesticide in a solventthat will hold the pesticide in solution. Oil solutions of a pesticideusually provide faster knockdown and kill of pests than otherformulations due to the solvents themselves having pesticidal action andthe dissolution of the waxy covering of the integument increasing thespeed of uptake of the pesticide. Other advantages of oil solutionsinclude better storage stability, better penetration of crevices, andbetter adhesion to greasy surfaces.

Another embodiment is an oil-in-water emulsion, wherein the emulsioncomprises oily globules which are each provided with a lamellar liquidcrystal coating and are dispersed in an aqueous phase, wherein each oilyglobule comprises at least one compound which is agriculturally active,and is individually coated with a monolamellar or oligolamellar layercomprising: (1) at least one non-ionic lipophilic surface-active agent,(2) at least one non-ionic hydrophilic surface-active agent and (3) atleast one ionic surface-active agent, wherein the globules having a meanparticle diameter of less than 800 nanometers. Further information onthe embodiment is disclosed in U.S. patent publication 20070027034published Feb. 1, 2007, having patent application Ser. No. 11/495,228.For ease of use, this embodiment will be referred to as “OIWE”.

For further information consult “Insect Pest Management” 2nd Edition byD. Dent, copyright CAB International (2000). Additionally, for moredetailed information consult “Handbook of Pest Control—The Behavior,Life History, and Control of Household Pests” by Arnold Mallis, 9thEdition, copyright 2004 by GIE Media Inc.

Other Formulation Components

Generally, when the molecules disclosed in Formula One are used in aformulation, such formulation can also contain other components. Thesecomponents include, but are not limited to, (this is a non-exhaustiveand non-mutually exclusive list) wetters, spreaders, stickers,penetrants, buffers, sequestering agents, drift reduction agents,compatibility agents, anti-foam agents, cleaning agents, andemulsifiers. A few components are described forthwith.

A wetting agent is a substance that when added to a liquid increases thespreading or penetration power of the liquid by reducing the interfacialtension between the liquid and the surface on which it is spreading.Wetting agents are used for two main functions in agrochemicalformulations: during processing and manufacture to increase the rate ofwetting of powders in water to make concentrates for soluble liquids orsuspension concentrates; and during mixing of a product with water in aspray tank to reduce the wetting time of wettable powders and to improvethe penetration of water into water-dispersible granules. Examples ofwetting agents used in wettable powder, suspension concentrate, andwater-dispersible granule formulations are: sodium lauryl sulfate;sodium dioctyl sulfosuccinate; alkyl phenol ethoxylates; and aliphaticalcohol ethoxylates.

A dispersing agent is a substance which adsorbs onto the surface ofparticles and helps to preserve the state of dispersion of the particlesand prevents them from reaggregating. Dispersing agents are added toagrochemical formulations to facilitate dispersion and suspension duringmanufacture, and to ensure the particles redisperse into water in aspray tank. They are widely used in wettable powders, suspensionconcentrates and water-dispersible granules. Surfactants that are usedas dispersing agents have the ability to adsorb strongly onto a particlesurface and provide a charged or steric barrier to reaggregation ofparticles. The most commonly used surfactants are anionic, non-ionic, ormixtures of the two types. For wettable powder formulations, the mostcommon dispersing agents are sodium lignosulfonates. For suspensionconcentrates, very good adsorption and stabilization are obtained usingpolyelectrolytes, such as sodium naphthalene sulfonate formaldehydecondensates. Tristyrylphenol ethoxylate phosphate esters are also used.Non-ionics such as alkylarylethylene oxide condensates and EO-PO blockcopolymers are sometimes combined with anionics as dispersing agents forsuspension concentrates. In recent years, new types of very highmolecular weight polymeric surfactants have been developed as dispersingagents. These have very long hydrophobic ‘backbones’ and a large numberof ethylene oxide chains forming the ‘teeth’ of a ‘comb’ surfactant.These high molecular weight polymers can give very good long-termstability to suspension concentrates because the hydrophobic backboneshave many anchoring points onto the particle surfaces. Examples ofdispersing agents used in agrochemical formulations are: sodiumlignosulfonates; sodium naphthalene sulfonate formaldehyde condensates;tristyrylphenol ethoxylate phosphate esters; aliphatic alcoholethoxylates; alkyl ethoxylates; EO-PO block copolymers; and graftcopolymers.

An emulsifying agent is a substance which stabilizes a suspension ofdroplets of one liquid phase in another liquid phase. Without theemulsifying agent the two liquids would separate into two immiscibleliquid phases. The most commonly used emulsifier blends containalkylphenol or aliphatic alcohol with twelve or more ethylene oxideunits and the oil-soluble calcium salt of dodecylbenzenesulfonic acid. Arange of hydrophile-lipophile balance (“HLB”) values from 8 to 18 willnormally provide good stable emulsions. Emulsion stability can sometimesbe improved by the addition of a small amount of an EO-PO blockcopolymer surfactant.

A solubilizing agent is a surfactant which will form micelles in waterat concentrations above the critical micelle concentration. The micellesare then able to dissolve or solubilize water-insoluble materials insidethe hydrophobic part of the micelle. The types of surfactants usuallyused for solubilization are non-ionics, sorbitan monooleates, sorbitanmonooleate ethoxylates, and methyl oleate esters.

Surfactants are sometimes used, either alone or with other additivessuch as mineral or vegetable oils as adjuvants to spray-tank mixes toimprove the biological performance of the pesticide on the target. Thetypes of surfactants used for bioenhancement depend generally on thenature and mode of action of the pesticide. However, they are oftennon-ionics such as: alkyl ethoxylates; linear aliphatic alcoholethoxylates; aliphatic amine ethoxylates.

A carrier or diluent in an agricultural formulation is a material addedto the pesticide to give a product of the required strength. Carriersare usually materials with high absorptive capacities, while diluentsare usually materials with low absorptive capacities. Carriers anddiluents are used in the formulation of dusts, wettable powders,granules and water-dispersible granules.

Organic solvents are used mainly in the formulation of emulsifiableconcentrates, oil-in-water emulsions, suspoemulsions, and ultra lowvolume formulations, and to a lesser extent, granular formulations.Sometimes mixtures of solvents are used. The first main groups ofsolvents are aliphatic paraffinic oils such as kerosene or refinedparaffins. The second main group (and the most common) comprises thearomatic solvents such as xylene and higher molecular weight fractionsof C9 and C10 aromatic solvents. Chlorinated hydrocarbons are useful ascosolvents to prevent crystallization of pesticides when the formulationis emulsified into water. Alcohols are sometimes used as cosolvents toincrease solvent power. Other solvents may include vegetable oils, seedoils, and esters of vegetable and seed oils.

Thickeners or gelling agents are used mainly in the formulation ofsuspension concentrates, emulsions and suspoemulsions to modify therheology or flow properties of the liquid and to prevent separation andsettling of the dispersed particles or droplets. Thickening, gelling,and anti-settling agents generally fall into two categories, namelywater-insoluble particulates and water-soluble polymers. It is possibleto produce suspension concentrate formulations using clays and silicas.Examples of these types of materials, include, but are not limited to,montmorillonite, bentonite, magnesium aluminum silicate, andattapulgite. Water-soluble polysaccharides have been used asthickening-gelling agents for many years. The types of polysaccharidesmost commonly used are natural extracts of seeds and seaweeds or aresynthetic derivatives of cellulose. Examples of these types of materialsinclude, but are not limited to, guar gum; locust bean gum; carrageenam;alginates; methyl cellulose; sodium carboxymethyl cellulose (SCMC);hydroxyethyl cellulose (HEC). Other types of anti-settling agents arebased on modified starches, polyacrylates, polyvinyl alcohol andpolyethylene oxide. Another good anti-settling agent is xanthan gum.

Microorganisms can cause spoilage of formulated products. Thereforepreservation agents are used to eliminate or reduce their effect.Examples of such agents include, but are not limited to: propionic acidand its sodium salt; sorbic acid and its sodium or potassium salts;benzoic acid and its sodium salt; p-hydroxybenzoic acid sodium salt;methyl p-hydroxybenzoate; and 1,2-benzisothiazolin-3-one (BIT).

The presence of surfactants often causes water-based formulations tofoam during mixing operations in production and in application through aspray tank. In order to reduce the tendency to foam, anti-foam agentsare often added either during the production stage or before fillinginto bottles. Generally, there are two types of anti-foam agents, namelysilicones and non-silicones. Silicones are usually aqueous emulsions ofdimethyl polysiloxane, while the non-silicone anti-foam agents arewater-insoluble oils, such as octanol and nonanol, or silica. In bothcases, the function of the anti-foam agent is to displace the surfactantfrom the air-water interface.

“Green” agents (e.g., adjuvants, surfactants, solvents) can reduce theoverall environmental footprint of crop protection formulations. Greenagents are biodegradable and generally derived from natural and/orsustainable sources, e.g. plant and animal sources. Specific examplesare: vegetable oils, seed oils, and esters thereof, also alkoxylatedalkyl polyglucosides.

For further information, see “Chemistry and Technology of AgrochemicalFormulations” edited by D. A. Knowles, copyright 1998 by Kluwer AcademicPublishers. Also see “Insecticides in Agriculture and EnvironmentRetrospects and Prospects” by A. S. Perry, I. Yamamoto, I. Ishaaya, andR. Perry, copyright 1998 by Springer-Verlag.

Pests

In general, the molecules of Formula One, Two, Three, and Four may beused to control pests e.g. beetles, earwigs, cockroaches, flies, aphids,scales, whiteflies, leafhoppers, ants, wasps, termites, moths,butterflies, lice, grasshoppers, locusts, crickets, fleas, thrips,bristletails, mites, ticks, nematodes, and symphylans.

In another embodiment, the Molecules of Formula One, Two, Three, andFour may be used to control pests in the Phyla Nematoda and/orArthropoda.

In another embodiment, the molecules of Formula One, Two, Three, andFour may be used to control pests in the Subphyla Chelicerata,Myriapoda, and/or Hexapoda.

In another embodiment, the molecules of Formula One, Two, Three, andFour may be used to control pests in the Classes of Arachnida, Symphyla,and/or Insecta.

In another embodiment, the molecules of Formula One, Two, Three, andFour may be used to control pests of the Order Anoplura. Anon-exhaustive list of particular genera includes, but is not limitedto, Haematopinus spp., Hoplopleura spp., Linognathus spp., Pediculusspp., and Polyplax spp. A non-exhaustive list of particular speciesincludes, but is not limited to, Haematopinus asini, Haematopinus suis,Linognathus setosus, Linognathus ovillus, Pediculus humanus capitis,Pediculus humanus humanus, and Pthirus pubis.

In another embodiment, the molecules of Formula One, Two, Three, andFour may be used to control pests in the Order Coleoptera. Anon-exhaustive list of particular genera includes, but is not limitedto, Acanthoscelides spp., Agriotes spp., Anthonomus spp., Apion spp.,Apogonia spp., Aulacophora spp., Bruchus spp., Cerosterna spp., Cerotomaspp., Ceutorhynchus spp., Chaetocnema spp., Colaspis spp., Cteniceraspp., Curculio spp., Cyclocephala spp., Diabrotica spp., Hypera spp.,Ips spp., Lyctus spp., Megascelis spp., Meligethes spp., Otiorhynchusspp., Pantomorus spp., Phyllophaga spp., Phyllotreta spp., Rhizotrogusspp., Rhynchites spp., Rhynchophorus spp., Scolytus spp., Sphenophorusspp., Sitophilus spp., and Tribolium spp. A non-exhaustive list ofparticular species includes, but is not limited to, Acanthoscelidesobtectus, Agrilus planipennis, Anoplophora glabripennis, Anthonomusgrandis, Ataenius spretulus, Atomaria linearis, Bothynoderespunctiventris, Bruchus pisorum, Callosobruchus maculatus, Carpophilushemipterus, Cassida vittata, Cerotoma trifurcata, Ceutorhynchusassimilis, Ceutorhynchus napi, Conoderus scalaris, Conoderus stigmosus,Conotrachelus nenuphar, Cotinis nitida, Crioceris asparagi, Cryptolestesferrugineus, Cryptolestes pusillus, Cryptolestes turcicus,Cylindrocopturus adspersus, Deporaus marginatus, Dermestes lardarius,Dermestes maculatus, Epilachna varivestis, Faustinus cubae, Hylobiuspales, Hypera postica, Hypothenemus hampei, Lasioderma serricorne,Leptinotarsa decemlineata, Liogenys fuscus, Liogenys suturalis,Lissorhoptrus oryzophilus, Maecolaspis joliveti, Melanotus communis,Meligethes aeneus, Melolontha melolontha, Oberea brevis, Oberealinearis, Oryctes rhinoceros, Oryzaephilus mercator, Oryzaephilussurinamensis, Oulema melanopus, Oulema oryzae, Phyllophaga cuyabana,Popillia japonica, Prostephanus truncatus, Rhyzopertha dominica Sitonalineatus, Sitophilus granarius, Sitophilus oryzae, Sitophilus zeamais,Stegobium paniceum, Tribolium castaneum, Tribolium confusum, Trogodermavariabile, and Zabrus tenebrioides.

In another embodiment, the molecules of Formula One, Two, Three, andFour may be used to control pests of the Order Dermaptera.

In another embodiment, the molecules of Formula One, Two, Three, andFour may be used to control pests of the Order Blattaria. Anon-exhaustive list of particular species includes, but is not limitedto, Blattella germanica, Blatta orientalis, Parcoblatta pennsylvanica,Periplaneta americana, Periplaneta australasiae, Periplaneta brunnea,Periplaneta fuliginosa, Pycnoscelus surinamensis, and Supellalongipalpa.

In another embodiment, the molecules of Formula One, Two, Three, andFour may be used to control pests of the Order Diptera. A non-exhaustivelist of particular genera includes, but is not limited to, Aedes spp.,Agromyza spp., Anastrepha spp., Anopheles spp., Bactrocera spp.,Ceratitis spp., Chrysops spp., Cochliomyia spp., Contarinia spp., Culexspp., Dasineura spp., Delia spp., Drosophila spp., Fannia spp., Hylemyiaspp., Liriomyza spp., Musca spp., Phorbia spp., Tabanus spp., and Tipulaspp. A non-exhaustive list of particular species includes, but is notlimited to, Agromyza frontella, Anastrepha suspensa, Anastrepha ludens,Anastrepha obliqa, Bactrocera cucurbitae, Bactrocera dorsalis,Bactrocera invadens, Bactrocera zonata, Ceratitis capitata, Dasineurabrassicae, Delia platura, Fannia canicularis, Fannia scalaris,Gasterophilus intestinalis, Gracillia perseae, Haematobia irritans,Hypoderma lineatum, Liriomyza brassicae, Melophagus ovinus, Muscaautumnalis, Musca domestica, Oestrus ovis, Oscinella frit, Pegomyabetae, Psila rosae, Rhagoletis cerasi, Rhagoletis pomonella, Rhagoletismendax, Sitodiplosis mosellana, and Stomoxys calcitrans.

In another embodiment, the molecules of Formula One, Two, Three, andFour may be used to control pests of the Order Hemiptera. Anon-exhaustive list of particular genera includes, but is not limitedto, Adelges spp., Aulacaspis spp., Aphrophora spp., Aphis spp., Bemisiaspp., Ceroplastes spp., Chionaspis spp., Chrysomphalus spp., Coccusspp., Empoasca spp., Lepidosaphes spp., Lagynotomus spp., Lygus spp.,Macrosiphum spp., Nephotettix spp., Nezara spp., Philaenus spp.,Phytocoris spp., Piezodorus spp., Planococcus spp., Pseudococcus spp.,Rhopalosiphum spp., Saissetia spp., Therioaphis spp., Toumeyella spp.,Toxoptera spp., Trialeurodes spp., Triatoma spp. and Unaspis spp. Anon-exhaustive list of particular species includes, but is not limitedto, Acrosternum hilare, Acyrthosiphon pisum, Aleyrodes proletella,Aleurodicus dispersus, Aleurothrixus floccosus, Amrasca biguttulabiguttula, Aonidiella aurantii, Aphis gossypii, Aphis glycines, Aphispomi, Aulacorthum solani, Bemisia argentifolii, Bemisia tabaci, Blissusleucopterus, Brachycorynella asparagi, Brevennia rehi, Brevicorynebrassicae, Calocoris norvegicus, Ceroplastes rubens, Cimex hemipterus,Cimex lectularius, Dagbertus fasciatus, Dichelops furcatus, Diuraphisnoxia, Diaphorina citri, Dysaphis plantaginea, Dysdercus suturellus,Edessa meditabunda, Eriosoma lanigerum, Eurygaster maura, Euschistusheros, Euschistus servus, Helopeltis antonii, Helopeltis theivora,Icerya purchasi, Idioscopus nitidulus, Laodelphax striatellus,Leptocorisa oratorius, Leptocorisa varicornis, Lygus hesperus,Maconellicoccus hirsutus, Macrosiphum euphorbiae, Macrosiphum granarium,Macrosiphum rosae, Macrosteles quadrilineatus, Mahanarva frimbiolata,Metopolophium dirhodum, Mictis longicornis, Myzus persicae, Nephotettixcinctipes, Neurocolpus longirostris, Nezara viridula, Nilaparvatalugens, Parlatoria pergandii, Parlatoria ziziphi, Peregrinus maidis,Phylloxera vitifoliae, Physokermes piceae Phytocoris californicus,Phytocoris relativus, Piezodorus guildinii, Poecilocapsus lineatus,Psallus vaccinicola, Pseudacysta perseae, Pseudococcus brevipes,Quadraspidiotus perniciosus, Rhopalosiphum maidis, Rhopalosiphum padi,Saissetia oleae, Scaptocoris castanea, Schizaphis graminum, Sitobionavenae, Sogatella furcifera, Trialeurodes vaporariorum, Trialeurodesabutiloneus, Unaspis yanonensis, and Zulia entrerriana.

In another embodiment, the molecules of Formula One, Two, Three, andFour may be used to control pests of the Order Hymenoptera. Anon-exhaustive list of particular genera includes, but is not limitedto, Acromyrmex spp., Atta spp., Camponotus spp., Diprion spp., Formicaspp., Monomorium spp., Neodiprion spp., Pogonomyrmex spp., Polistesspp., Solenopsis spp., Vespula spp., and Xylocopa spp. A non-exhaustivelist of particular species includes, but is not limited to, Athaliarosae, Atta texana, Iridomyrmex humilis, Monomorium minimum, Monomoriumpharaonis, Solenopsis invicta, Solenopsis geminata, Solenopsis molesta,Solenopsis richtery, Solenopsis xyloni, and Tapinoma sessile.

In another embodiment, the molecules of Formula One, Two, Three, andFour may be used to control pests of the Order Isoptera. Anon-exhaustive list of particular genera includes, but is not limitedto, Coptotermes spp., Cornitermes spp., Cryptotermes spp., Heterotermesspp., Kalotermes spp., Incisitermes spp., Macrotermes spp.,Marginitermes spp., Microcerotermes spp., Procornitermes spp.,Reticulitermes spp., Schedorhinotermes spp., and Zootermopsis spp. Anon-exhaustive list of particular species includes, but is not limitedto, Coptotermes curvignathus, Coptotermes frenchi, Coptotermesformosanus, Heterotermes aureus, Microtermes obesi, Reticulitermesbanyulensis, Reticulitermes grassei, Reticulitermes flavipes,Reticulitermes hageni, Reticulitermes hesperus, Reticulitermessantonensis, Reticulitermes speratus, Reticulitermes tibialis, andReticulitermes virginicus.

In another embodiment, the molecules of Formula One, Two, Three, andFour may be used to control pests of the Order Lepidoptera. Anon-exhaustive list of particular genera includes, but is not limitedto, Adoxophyes spp., Agrotis spp., Argyrotaenia spp., Cacoecia spp.,Caloptilia spp., Chilo spp., Chrysodeixis spp., Colias spp., Crambusspp., Diaphania spp., Diatraea spp., Earias spp., Ephestia spp.,Epimecis spp., Feltia spp., Gortyna spp., Helicoverpa spp., Heliothisspp., Indarbela spp., Lithocolletis spp., Loxagrotis spp., Malacosomaspp., Peridroma spp., Phyllonorycter spp., Pseudaletia spp., Sesamiaspp., Spodoptera spp., Synanthedon spp., and Yponomeuta spp. Anon-exhaustive list of particular species includes, but is not limitedto, Achaea janata, Adoxophyes orana, Agrotis ipsilon, Alabamaargillacea, Amorbia cuneana, Amyelois transitella, Anacamptodesdefectaria, Anarsia lineatella, Anomis sabulifera, Anticarsiagemmatalis, Archips argyrospila, Archips rosana, Argyrotaenia citrana,Autographa gamma, Bonagota cranaodes, Borbo cinnara, Bucculatrixthurberiella, Capua reticulana, Carposina niponensis, Chlumetiatransversa, Choristoneura rosaceana, Cnaphalocrocis medinalis,Conopomorpha cramerella, Cossus cossus, Cydia caryana, Cydia funebrana,Cydia molesta, Cydia nigricana, Cydia pomonella, Darna diducta, Diatraeasaccharalis, Diatraea grandiosella, Earias insulana, Earias vittella,Ecdytolopha aurantianum, Elasmopalpus lignosellus, Ephestia cautella,Ephestia elutella, Ephestia kuehniella, Epinotia aporema, Epiphyaspostvittana, Erionota thrax, Eupoecilia ambiguella, Euxoa auxiliaris,Grapholita molesta, Hedylepta indicata, Helicoverpa armigera,Helicoverpa zea, Heliothis virescens, Hellula undalis, Keiferialycopersicella, Leucinodes orbonalis, Leucoptera coffeella, Leucopteramalifoliella, Lobesia botrana, Loxagrotis albicosta, Lymantria dispar,Lyonetia clerkella, Mahasena corbetti, Mamestra brassicae, Marucatestulalis, Metisa plana, Mythimna unipuncta, Neoleucinodes elegantalis,Nymphula depunctalis, Operophtera brumata, Ostrinia nubilalis, Oxydiavesulia, Pandemis cerasana, Pandemis heparana, Papilio demodocus,Pectinophora gossypiella, Peridroma saucia, Perileucoptera coffeella,Phthorimaea operculella, Phyllocnistis citrella, Pieris rapae,Plathypena scabra, Plodia interpunctella, Plutella xylostella,Polychrosis viteana, Prays endocarpa, Prays oleae, Pseudaletiaunipuncta, Pseudoplusia includens, Rachiplusia nu, Scirpophagaincertulas, Sesamia inferens, Sesamia nonagrioides, Setora nitens,Sitotroga cerealella, Sparganothis pilleriana, Spodoptera exigua,Spodoptera frugiperda, Spodoptera eridania, Thecla basilides, Tineolabisselliella, Trichoplusia ni, Tuta absoluta, Zeuzera coffeae, andZeuzera pyrina.

In another embodiment, the molecules of Formula One, Two, Three, andFour may be used to control pests of the Order Mallophaga. Anon-exhaustive list of particular genera includes, but is not limitedto, Anaticola spp., Bovicola spp., Chelopistes spp., Goniodes spp.,Menacanthus spp., and Trichodectes spp. A non-exhaustive list ofparticular species includes, but is not limited to, Bovicola bovis,Bovicola caprae, Bovicola ovis, Chelopistes meleagridis, Goniodesdissimilis, Goniodes gigas, Menacanthus stramineus, Menopon gallinae,and Trichodectes canis.

In another embodiment, the molecules of Formula One, Two, Three, andFour may be used to control pests of the Order Orthoptera. Anon-exhaustive list of particular genera includes, but is not limitedto, Melanoplus spp., and Pterophylla spp. A non-exhaustive list ofparticular species includes, but is not limited to, Anabrus simplex,Gryllotalpa africana, Gryllotalpa australis, Gryllotalpa brachyptera,Gryllotalpa hexadactyla, Locusta migratoria, Microcentrum retinerve,Schistocerca gregaria, and Scudderia furcata.

In another embodiment, the molecules of Formula One, Two, Three, andFour may be used to control pests of the Order Siphonaptera. Anon-exhaustive list of particular species includes, but is not limitedto, Ceratophyllus gallinae, Ceratophyllus niger, Ctenocephalides canis,Ctenocephalides felis, and Pulex irritans.

In another embodiment, the molecules of Formula One, Two, Three, andFour may be used to control pests of the Order Thysanoptera. Anon-exhaustive list of particular genera includes, but is not limitedto, Caliothrips spp., Frankliniella spp., Scirtothrips spp., and Thripsspp. A non-exhaustive list of particular sp. includes, but is notlimited to, Frankliniella fusca, Frankliniella occidentalis,Frankliniella schultzei, Frankliniella williamsi, Heliothripshaemorrhoidalis, Rhipiphorothrips cruentatus, Scirtothrips citri,Scirtothrips dorsalis, and Taeniothrips rhopalantennalis, Thripshawaiiensis, Thrips nigropilosus, Thrips orientalis, Thrips tabaci.

In another embodiment, the molecules of Formula One, Two, Three, andFour may be used to control pests of the Order Thysanura. Anon-exhaustive list of particular genera includes, but is not limitedto, Lepisma spp. and Thermobia spp.

In another embodiment, the molecules of Formula One, Two, Three, andFour may be used to control pests of the Order Acarina. A non-exhaustivelist of particular genera includes, but is not limited to, Acarus spp.,Aculops spp., Boophilus spp., Demodex spp., Dermacentor spp.,Epitrimerus spp., Eriophyes spp., Ixodes spp., Oligonychus spp.,Panonychus spp., Rhizoglyphus spp., and Tetranychus spp. Anon-exhaustive list of particular species includes, but is not limitedto, Acarapis woodi, Acarus siro, Aceria mangiferae, Aculops lycopersici,Aculus pelekassi, Aculus schlechtendali, Amblyomma americanum,Brevipalpus obovatus, Brevipalpus phoenicis, Dermacentor variabilis,Dermatophagoides pteronyssinus, Eotetranychus carpini, Notoedres cati,Oligonychus coffeae, Oligonychus ilicis, Panonychus citri, Panonychusulmi, Phyllocoptruta oleivora, Polyphagotarsonemus latus, Rhipicephalussanguineus, Sarcoptes scabiei, Tegolophus perseaflorae, Tetranychusurticae, and Varroa destructor.

In another embodiment, the molecules of Formula One, Two, Three, andFour may be used to control pest of the Order Symphyla. A non-exhaustivelist of particular sp. includes, but is not limited to, Scutigerellaimmaculata.

In another embodiment, the molecules of Formula One, Two, Three, andFour may be used to control pests of the Phylum Nematoda. Anon-exhaustive list of particular genera includes, but is not limitedto, Aphelenchoides spp., Belonolaimus spp., Criconemella spp.,Ditylenchus spp., Heterodera spp., Hirschmanniella spp., Hoplolaimusspp., Meloidogyne spp., Pratylenchus spp., and Radopholus spp. Anon-exhaustive list of particular sp. includes, but is not limited to,Dirofilaria immitis, Heterodera zeae, Meloidogyne incognita, Meloidogynejavanica, Onchocerca volvulus, Radopholus similis, and Rotylenchulusreniformis.

For additional information consult “HANDBOOK OF PEST CONTROL—THEBEHAVIOR, LIFE HISTORY, AND CONTROL OF HOUSEHOLD PESTS” by ArnoldMattis, 9th Edition, copyright 2004 by GIE Media Inc.

Applications

Molecules of Formula One, Two, Three, and Four are generally used inamounts from about 0.01 grams per hectare to about 5000 grams perhectare to provide control. Amounts from about 0.1 grams per hectare toabout 500 grams per hectare are generally preferred, and amounts fromabout 1 gram per hectare to about 50 grams per hectare are generallymore preferred.

The area to which a molecule of Formula One is applied can be any areainhabited (or maybe inhabited, or traversed by) a pest, for example:where crops, trees, fruits, cereals, fodder species, vines, turf andornamental plants, are growing; where domesticated animals are residing;the interior or exterior surfaces of buildings (such as places wheregrains are stored), the materials of construction used in building (suchas impregnated wood), and the soil around buildings. Particular cropareas to use a molecule of Formula One include areas where apples, corn,sunflowers, cotton, soybeans, canola, wheat, rice, sorghum, barley,oats, potatoes, oranges, alfalfa, lettuce, strawberries, tomatoes,peppers, crucifers, pears, tobacco, almonds, sugar beets, beans andother valuable crops are growing or the seeds thereof are going to beplanted. It is also advantageous to use aluminum sulfate with a moleculeof Formula One when growing various plants.

Controlling pests generally means that pest populations, pest activity,or both, are reduced in an area. This can come about when: pestpopulations are repulsed from an area; when pests are incapacitated inor around an area; or pests are exterminated, in whole, or in part, inor around an area. Of course, a combination of these results can occur.Generally, pest populations, activity, or both are desirably reducedmore than fifty percent, preferably more than 90 percent. Generally, thearea is not in or on a human; consequently, the locus is generally anon-human area.

The molecules of Formula One, Two, Three, and Four may be used inmixtures, applied simultaneously or sequentially, alone or with othercompounds to enhance plant vigor (e.g. to grow a better root system, tobetter withstand stressful growing conditions). Such other compoundsare, for example, compounds that modulate plant ethylene receptors, mostnotably 1-methylcyclopropene (also known as 1-MCP).

The molecules of Formula One, Two, Three, and Four can be applied to thefoliar and fruiting portions of plants to control pests. The moleculeswill either come in direct contact with the pest, or the pest willconsume the pesticide when eating leaf, fruit mass, or extracting sap,that contains the pesticide. The molecules of Formula One, Two, Three,and Four can also be applied to the soil, and when applied in thismanner, root and stem feeding pests can be controlled. The roots canabsorb a molecule taking it up into the foliar portions of the plant tocontrol above ground chewing and sap feeding pests.

Generally, with baits, the baits are placed in the ground where, forexample, termites can come into contact with, and/or be attracted to,the bait. Baits can also be applied to a surface of a building,(horizontal, vertical, or slant surface) where, for example, ants,termites, cockroaches, and flies, can come into contact with, and/or beattracted to, the bait. Baits can comprise a molecule of Formula One.

The molecules of Formula One, Two, Three, and Four can be encapsulatedinside, or placed on the surface of a capsule. The size of the capsulescan range from nanometer size (about 100-900 nanometers in diameter) tomicrometer size (about 10-900 microns in diameter).

Because of the unique ability of the eggs of some pests to resistcertain pesticides, repeated applications of the molecules of FormulaOne, Two, Three, and Four may be desirable to control newly emergedlarvae.

Systemic movement of pesticides in plants may be utilized to controlpests on one portion of the plant by applying (for example by sprayingan area) the molecules of Formula One, Two, Three, and Four to adifferent portion of the plant. For example, control of foliar-feedinginsects can be achieved by drip irrigation or furrow application, bytreating the soil with for example pre- or post-planting soil drench, orby treating the seeds of a plant before planting.

Seed treatment can be applied to all types of seeds, including thosefrom which plants genetically modified to express specialized traitswill germinate. Representative examples include those expressingproteins toxic to invertebrate pests, such as Bacillus thuringiensis orother insecticidal toxins, those expressing herbicide resistance, suchas “Roundup Ready” seed, or those with “stacked” foreign genesexpressing insecticidal toxins, herbicide resistance,nutrition-enhancement, drought resistance, or any other beneficialtraits. Furthermore, such seed treatments with the molecules of FormulaOne, Two, Three, and Four may further enhance the ability of a plant tobetter withstand stressful growing conditions. This results in ahealthier, more vigorous plant, which can lead to higher yields atharvest time. Generally, about 1 gram of the molecules of Formula One,Two, Three, and Four to about 500 grams per 100,000 seeds is expected toprovide good benefits, amounts from about 10 grams to about 100 gramsper 100,000 seeds is expected to provide better benefits, and amountsfrom about 25 grams to about 75 grams per 100,000 seeds is expected toprovide even better benefits.

It should be readily apparent that the molecules of Formula One, Two,Three, and Four may be used on, in, or around plants geneticallymodified to express specialized traits, such as Bacillus thuringiensisor other insecticidal toxins, or those expressing herbicide resistance,or those with “stacked” foreign genes expressing insecticidal toxins,herbicide resistance, nutrition-enhancement, or any other beneficialtraits.

The molecules of Formula One, Two, Three, and Four may be used forcontrolling endoparasites and ectoparasites in the veterinary medicinesector or in the field of non-human animal keeping. The molecules ofFormula One, Two, Three, and Four are applied, such as by oraladministration in the form of, for example, tablets, capsules, drinks,granules, by dermal application in the form of, for example, dipping,spraying, pouring on, spotting on, and dusting, and by parenteraladministration in the form of, for example, an injection.

The molecules of Formula One, Two, Three, and Four may also be employedadvantageously in livestock keeping, for example, cattle, sheep, pigs,chickens, and geese. They may also be employed advantageously in petssuch as, horses, dogs, and cats. Particular pests to control would befleas and ticks that are bothersome to such animals. Suitableformulations are administered orally to the animals with the drinkingwater or feed. The dosages and formulations that are suitable depend onthe species.

The molecules of Formula One, Two, Three, and Four may also be used forcontrolling parasitic worms, especially of the intestine, in the animalslisted above.

The molecules of Formula One, Two, Three, and Four may also be employedin therapeutic methods for human health care. Such methods include, butare limited to, oral administration in the form of, for example,tablets, capsules, drinks, granules, and by dermal application.

Pests around the world have been migrating to new environments (for suchpest) and thereafter becoming a new invasive species in such newenvironment. The molecules of Formula One, Two, Three, and Four may alsobe used on such new invasive species to control them in such newenvironment.

The molecules of Formula One, Two, Three, and Four may also be used inan area where plants, such as crops, are growing (e.g. pre-planting,planting, pre-harvesting) and where there are low levels (even no actualpresence) of pests that can commercially damage such plants. The use ofsuch molecules in such area is to benefit the plants being grown in thearea. Such benefits, may include, but are not limited to, improving thehealth of a plant, improving the yield of a plant (e.g. increasedbiomass and/or increased content of valuable ingredients), improving thevigor of a plant (e.g. improved plant growth and/or greener leaves),improving the quality of a plant (e.g. improved content or compositionof certain ingredients), and improving the tolerance to abiotic and/orbiotic stress of the plant.

Before a pesticide can be used or sold commercially, such pesticideundergoes lengthy evaluation processes by various governmentalauthorities (local, regional, state, national, and international).Voluminous data requirements are specified by regulatory authorities andmust be addressed through data generation and submission by the productregistrant or by a third party on the product registrant's behalf, oftenusing a computer with a connection to the World Wide Web. Thesegovernmental authorities then review such data and if a determination ofsafety is concluded, provide the potential user or seller with productregistration approval. Thereafter, in that locality where the productregistration is granted and supported, such user or seller may use orsell such pesticide.

A molecules according to Formula One, Two, Three, and Four can be testedto determine its efficacy against pests. Furthermore, mode of actionstudies can be conducted to determine if said molecule has a differentmode of action than other pesticides. Thereafter, such acquired data canbe disseminated, such as by the internet, to third parties.

The headings in this document are for convenience only and must not beused to interpret any portion hereof.

TABLE SECTION % Control (or Mortality) Rating BAW & CEW Rating Table50-100 A More than 0-Less than 50 B Not Tested C No activity noticed inthis bioassay D GPA Rating Table 80-100 A More than 0-Less than 80 B NotTested C No activity noticed in this bioassay D

TABLE Bio Results Compound % Mortality % Mortality % Mortality NumberBAW 50 μg/cm² CEW 50 μg/cm² GPA 200 ppm 1 A A D 2 A A B 3 A A B 4 A A D5 A A D 6 A A B 7 A A D 8 A A B 9 A A D 10 A A B 11 A A B 12 A A B 13 AA D 14 A A B 15 C C B 16 C C D 17 A A D 18 D B D 19 D A B 20 A A B 21 AA D 22 A A D 23 D A B 24 A D B 25 D D B 26 A B D 27 B A D 28 D D B 29 AA D 30 D D B 31 D D D 32 D A B

We claim:
 1. A pesticidal composition comprising a molecule according toFormula One

wherein: (a) Ar₁ is (1) phenyl or (2) substituted phenyl, wherein saidsubstituted phenyl has one or more substituents independently selectedfrom H, F, Cl, Br, I, CN, NO₂, C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₃-C₆cycloalkyl, C₃-C₆ halocycloalkyl, C₃-C₆ cycloalkoxy, C₃-C₆halocycloalkoxy, C₁-C₆ alkoxy, C₁-C₆ haloalkoxy, C₂-C₆ alkenyl, C₂-C₆alkynyl, S(═O)_(n)(C₁-C₆ alkyl), S(═O)_(n)(C₁-C₆ haloalkyl), OSO₂(C₁-C₆alkyl), OSO₂(C₁-C₆ haloalkyl), C(═O)NR_(x)R_(y), (C₁-C₆alkyl)NR_(x)R_(y), C(═O)(C₁-C₆ alkyl), C(═O)O(C₁-C₆ alkyl), C(═O)(C₁-C₆haloalkyl), C(═O)O(C₁-C₆ haloalkyl), C(═O)(C₃-C₆ cycloalkyl),C(═O)O(C₃-C₆ cycloalkyl), C(═O)(C₂-C₆ alkenyl), C(═O)O(C₂-C₆ alkenyl),(C₁-C₆ alkyl)O(C₁-C₆ alkyl), (C₁-C₆ alkyl)S(C₁-C₆ alkyl), C(═O)(C₁-C₆alkyl)C(═O)O(C₁-C₆ alkyl), phenyl, phenoxy, substituted phenyl, andsubstituted phenoxy, wherein such substituted phenyl and substitutedphenoxy have one or more substituents independently selected from H, F,Cl, Br, I, CN, NO₂, C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₁-C₆ hydroxyalkyl,C₃-C₆ cycloalkyl, C₃-C₆ halocycloalkyl, C₃-C₆ hydroxycycloalkyl, C₃-C₆cycloalkoxy, C₃-C₆ halocycloalkoxy, C₃-C₆ hydroxycycloalkoxy, C₁-C₆alkoxy, C₁-C₆ haloalkoxy, C₂-C₆ alkenyl, C₂-C₆ alkynyl, S(═O)_(n)(C₁-C₆alkyl), S(═O)_(n)(C₁-C₆ haloalkyl), OSO₂(C₁-C₆ alkyl), OSO₂(C₁-C₆haloalkyl), C(═O)NR_(x)R_(y), (C₁-C₆ alkyl)NR_(x)R_(y), C(═O)(C₁-C₆alkyl), C(═O)O(C₁-C₆ alkyl), C(═O)(C₁-C₆ haloalkyl), C(═O)O(C₁-C₆haloalkyl), C(═O)(C₃-C₆ cycloalkyl), C(═O)O(C₃-C₆ cycloalkyl),C(═O)(C₂-C₆ alkenyl), C(═O)O(C₂-C₆ alkenyl), (C₁-C₆ alkyl)O(C₁-C₆alkyl), (C₁-C₆ alkyl)S(C₁-C₆ alkyl), C(═O)(C₁-C₆ alkyl)C(═O)O(C₁-C₆alkyl) phenyl, and phenoxy; (b) Het is a 1,2,4-triazolyl, where Ar₁ andAr₂ are not ortho to each other, and where said triazolyl may besubstituted with one or more substituents independently selected from H,OH, F, Cl, Br, I, CN, NO₂, oxo, C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₁-C₆hydroxyalkyl, C₃-C₆ cycloalkyl, C₃-C₆ halocycloalkyl, C₃-C₆hydroxycycloalkyl, C₃-C₆ cycloalkoxy, C₃-C₆ halocycloalkoxy, C₃-C₆hydroxycycloalkoxy, C₁-C₆ alkoxy, C₁-C₆ haloalkoxy, C₂-C₆ alkenyl, C₂-C₆alkynyl, S(═O)_(n)(C₁-C₆ alkyl), S(═O)_(n)(C₁-C₆ haloalkyl), OSO₂(C₁-C₆alkyl), OSO₂(C₁-C₆ haloalkyl), C(═O)NR_(x)R_(y), (C₁-C₆alkyl)NR_(x)R_(y), C(═O)(C₁-C₆ alkyl), C(═O)O(C₁-C₆ alkyl), C(═O)(C₁-C₆haloalkyl), C(═O)O(C₁-C₆ haloalkyl), C(═O)(C₃-C₆ cycloalkyl),C(═O)O(C₃-C₆ cycloalkyl), C(═O)(C₂-C₆ alkenyl), C(═O)O(C₂-C₆ alkenyl),(C₁-C₆ alkyl)O(C₁-C₆ alkyl), (C₁-C₆ alkyl)S(C₁-C₆ alkyl), C(═O)(C₁-C₆alkyl)C(═O)O(C₁-C₆ alkyl), phenyl, phenoxy, substituted phenyl andsubstituted phenoxy wherein such substituted phenyl and substitutedphenoxy have one or more substituents independently selected from H, OH,F, Cl, Br, I, CN, NO₂, C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₁-C₆ hydroxyalkyl,C₃-C₆ cycloalkyl, C₃-C₆ halocycloalkyl, C₃-C₆ hydroxycycloalkyl, C₃-C₆cycloalkoxy, C₃-C₆ halocycloalkoxy, C₃-C₆ hydroxycycloalkoxy, C₁-C₆alkoxy, C₁-C₆ haloalkoxy, C₂-C₆ alkenyl, C₂-C₆ alkynyl, S(═O)_(n)(C₁-C₆alkyl), S(═O)_(n)(C₁-C₆ haloalkyl), OSO₂(C₁-C₆ alkyl), OSO₂(C₁-C₆haloalkyl), C(═O)H, C(═O)OH, C(═O)NR_(x)R_(y), (C₁-C₆ alkyl)NR_(x)R_(y),C(═O)(C₁-C₆ alkyl), C(═O)O(C₁-C₆ alkyl), C(═O)(C₁-C₆ haloalkyl),C(═O)O(C₁-C₆ haloalkyl), C(═O)(C₃-C₆ cycloalkyl), C(═O)O(C₃-C₆cycloalkyl), C(═O)(C₂-C₆ alkenyl), C(═O)O(C₂-C₆ alkenyl), (C₁-C₆alkyl)O(C₁-C₆ alkyl), (C₁-C₆ alkyl)S(C₁-C₆ alkyl), C(═O)(C₁-C₆alkyl)C(═O)O(C₁-C₆ alkyl), phenyl, and phenoxy; (c) Ar₂ is (1) phenyl,or (2) substituted phenyl, wherein said substituted phenyl, has one ormore substituents independently selected from H, OH, F, Cl, Br, I, CN,NO₂, C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₁-C₆ hydroxyalkyl, C₃-C₆ cycloalkyl,C₃-C₆ halocycloalkyl, C₃-C₆ hydroxycycloalkyl, C₃-C₆ cycloalkoxy, C₃-C₆halocycloalkoxy, C₃-C₆ hydroxycycloalkoxy, C₁-C₆ alkoxy, C₁-C₆haloalkoxy, C₂-C₆ alkenyl, C₂-C₆ alkynyl, S(═O)_(n)(C₁-C₆ alkyl),S(═O)_(n)(C₁-C₆ haloalkyl), OSO₂(C₁-C₆ alkyl), OSO₂(C₁-C₆ haloalkyl),C(═O)NR_(x)R_(y), (C₁-C₆ alkyl)NR_(x)R_(y), C(═O)(C₁-C₆ alkyl),C(═O)O(C₁-C₆ alkyl), C(═O)(C₁-C₆ haloalkyl), C(═O)O(C₁-C₆ haloalkyl),C(═O)(C₃-C₆ cycloalkyl), C(═O)O(C₃-C₆ cycloalkyl), C(═O)(C₂-C₆ alkenyl),C(═O)O(C₂-C₆ alkenyl), (C₁-C₆ alkyl)O(C₁-C₆ alkyl), (C₁-C₆ alkyl)S(C₁-C₆alkyl), C(═O)(C₁-C₆ alkyl)C(═O)O(C₁-C₆ alkyl), phenyl, phenoxy,substituted phenyl and substituted phenoxy wherein such substitutedphenyl and substituted phenoxy have one or more substituentsindependently selected from H, OH, F, Cl, Br, I, CN, NO₂, C₁-C₆ alkyl,C₁-C₆ haloalkyl, C₁-C₆ hydroxyalkyl, C₃-C₆ cycloalkyl, C₃-C₆halocycloalkyl, C₃-C₆ hydroxycycloalkyl, C₃-C₆ cycloalkoxy, C₃-C₆halocycloalkoxy, C₃-C₆ hydroxycycloalkoxy, C₁-C₆ alkoxy, C₁-C₆haloalkoxy, C₂-C₆ alkenyl, C₂-C₆ alkynyl, S(═O)_(n)(C₁-C₆ alkyl),S(═O)_(n)(C₁-C₆ haloalkyl), OSO₂(C₁-C₆ alkyl), OSO₂(C₁-C₆ haloalkyl),C(═O)H, C(═O)OH, C(═O)NR_(x)R_(y), (C₁-C₆ alkyl)NR_(x)R_(y), C(═O)(C₁-C₆alkyl), C(═O)O(C₁-C₆ alkyl), C(═O)(C₁-C₆ haloalkyl), C(═O)O(C₁-C₆haloalkyl), C(═O)(C₃-C₆ cycloalkyl), C(═O)O(C₃-C₆ cycloalkyl),C(═O)(C₁-C₆ haloalkyl), C(═O)(C₂-C₆ alkenyl), C(═O)O(C₂-C₆ alkenyl),(C₁-C₆ alkyl)O(C₁-C₆ alkyl), (C₁-C₆ alkyl)S(C₁-C₆ alkyl), C(═O)(C₁-C₆alkyl)C(═O)O(C₁-C₆ alkyl), phenyl, and phenoxy); (d) R1 and R2 and thecarbons they are attached to form a cyclopropyl structure, where are thelinking carbon atom that is optionally substituted with one or moresubstituents independently selected from OH, F, Cl, Br, I, CN, NO₂, oxo,C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₁-C₆ hydroxyalkyl, C₃-C₆ cycloalkyl,C₃-C₆ halocycloalkyl, C₃-C₆ hydroxycycloalkyl, C₃-C₆ cycloalkoxy, C₃-C₆halocycloalkoxy, C₃-C₆ hydroxycycloalkoxy, C₁-C₆ alkoxy, C₁-C₆haloalkoxy, C₂-C₆ alkenyl, C₂-C₆ alkynyl, S(═O)_(n)(C₁-C₆ alkyl),S(═O)_(n)(C₁-C₆ haloalkyl), OSO₂(C₁-C₆ alkyl), OSO₂(C₁-C₆ haloalkyl),C(═O)NR_(x)R_(y), (C₁-C₆ alkyl)NR_(x)R_(y), C(═O)(C₁-C₆ alkyl),C(═O)O(C₁-C₆ alkyl), C(═O)(C₁-C₆ haloalkyl), C(═O)O(C₁-C₆ haloalkyl),C(═O)(C₃-C₆ cycloalkyl), C(═O)O(C₃-C₆ cycloalkyl), C(═O)(C₂-C₆ alkenyl),C(═O)O(C₂-C₆ alkenyl), (C₁-C₆ alkyl)O(C₁-C₆ alkyl), (C₁-C₆ alkyl)S(C₁-C₆alkyl), C(═O)(C₁-C₆ alkyl)C(═O)O(C₁-C₆ alkyl), phenyl, and phenoxy; (e)R3 is H, CN, F, Cl, Br, I, C₁-C₆ alkyl, C₃-C₆ cycloalkyl, C₃-C₆cycloalkoxy, C₁-C₆ alkoxy, C₂-C₆ alkenyl, C₂-C₆ alkynyl, S(═O)_(n)(C₁-C₆alkyl), OSO₂(C₁-C₆ alkyl), OSO₂(C₁-C₆ haloalkyl), C(═O)NR_(x)R_(y),(C₁-C₆ alkyl)NR_(x)R_(y), C(═O)(C₁-C₆ alkyl), C(═O)O(C₁-C₆ alkyl),C(═O)(C₁-C₆ haloalkyl), C(═O)O(C₁-C₆ haloalkyl), C(═O)(C₃-C₆cycloalkyl), C(═O)O(C₃-C₆ cycloalkyl), C(═O)(C₂-C₆ alkenyl),C(═O)O(C₂-C₆ alkenyl), (C₁-C₆ alkyl)O(C₁-C₆ alkyl), (C₁-C₆ alkyl)S(C₁-C₆alkyl), C(═O)(C₁-C₆ alkyl)C(═O)O(C₁-C₆ alkyl), phenyl, and phenoxy,wherein each alkyl, cycloalkyl, cycloalkoxy, alkoxy, alkenyl, alkynyl,phenyl, and phenoxy are optionally substituted with one or moresubstituents independently selected from OH, F, Cl, Br, I, CN, NO₂, oxo,C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₁-C₆ hydroxyalkyl, C₃-C₆ cycloalkyl,C₃-C₆ halocycloalkyl, C₃-C₆ hydroxycycloalkyl, C₃-C₆ cycloalkoxy, C₃-C₆halocycloalkoxy, C₃-C₆ hydroxycycloalkoxy, C₁-C₆ alkoxy, C₁-C₆haloalkoxy, C₂-C₆ alkenyl, C₂-C₆ alkynyl, S(═O)_(n)(C₁-C₆ alkyl),S(═O)_(n)(C₁-C₆ haloalkyl), OSO₂(C₁-C₆ alkyl), OSO₂(C₁-C₆ haloalkyl),C(═O)NR_(x)R_(y), (C₁-C₆ alkyl)NR_(x)R_(y), C(═O)(C₁-C₆ alkyl),C(═O)O(C₁-C₆ alkyl), C(═O)(C₁-C₆ haloalkyl), C(═O)O(C₁-C₆ haloalkyl),C(═O)(C₃-C₆ cycloalkyl), C(═O)O(C₃-C₆ cycloalkyl), C(═O)(C₂-C₆ alkenyl),C(═O)O(C₂-C₆ alkenyl), (C₁-C₆ alkyl)O(C₁-C₆ alkyl), (C₁-C₆ alkyl)S(C₁-C₆alkyl), C(═O)(C₁-C₆ alkyl)C(═O)O(C₁-C₆ alkyl), phenyl, and phenoxy; (f)R4 is H, CN, F, Cl, Br, I, C₁-C₆ alkyl, C₃-C₆ cycloalkyl, C₃-C₆cycloalkoxy, C₁-C₆ alkoxy, C₂-C₆ alkenyl, C₂-C₆ alkynyl, S(═O)_(n)(C₁-C₆alkyl), OSO₂(C₁-C₆ alkyl), OSO₂(C₁-C₆ haloalkyl), C(═O)NR_(x)R_(y),(C₁-C₆ alkyl)NR_(x)R_(y), C(═O)(C₁-C₆ alkyl), C(═O)O(C₁-C₆ alkyl),C(═O)(C₁-C₆ haloalkyl), C(═O)O(C₁-C₆ haloalkyl), C(═O)(C₃-C₆cycloalkyl), C(═O)O(C₃-C₆ cycloalkyl), C(═O)(C₂-C₆ alkenyl),C(═O)O(C₂-C₆ alkenyl), (C₁-C₆ alkyl)O(C₁-C₆ alkyl), (C₁-C₆ alkyl)S(C₁-C₆alkyl), C(═O)(C₁-C₆ alkyl)C(═O)O(C₁-C₆ alkyl), phenyl, and phenoxy,wherein each alkyl, cycloalkyl, cycloalkoxy, alkoxy, alkenyl, alkynyl,phenyl, and phenoxy are optionally substituted with one or moresubstituents independently selected from OH, F, Cl, Br, I, CN, NO₂, oxo,C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₁-C₆ hydroxyalkyl, C₃-C₆ cycloalkyl,C₃-C₆ halocycloalkyl, C₃-C₆ hydroxycycloalkyl, C₃-C₆ cycloalkoxy, C₃-C₆halocycloalkoxy, C₃-C₆ hydroxycycloalkoxy, C₁-C₆ alkoxy, C₁-C₆haloalkoxy, C₂-C₆ alkenyl, C₂-C₆ alkynyl, S(═O)_(n)(C₁-C₆ alkyl),S(═O)_(n)(C₁-C₆ haloalkyl), OSO₂(C₁-C₆ alkyl), OSO₂(C₁-C₆ haloalkyl),C(═O)NR_(x)R_(y), (C₁-C₆ alkyl)NR_(x)R_(y), C(═O)(C₁-C₆ alkyl),C(═O)O(C₁-C₆ alkyl), C(═O)(C₁-C₆ haloalkyl), C(═O)O(C₁-C₆ haloalkyl),C(═O)(C₃-C₆ cycloalkyl), C(═O)O(C₃-C₆ cycloalkyl), C(═O)(C₂-C₆ alkenyl),C(═O)O(C₂-C₆ alkenyl), (C₁-C₆ alkyl)O(C₁-C₆ alkyl), (C₁-C₆ alkyl)S(C₁-C₆alkyl), C(═O)(C₁-C₆ alkyl)C(═O)O(C₁-C₆ alkyl), phenyl, and phenoxy; (g)R5 is H, CN, F, Cl, Br, I, C₁-C₆ alkyl, C₃-C₆ cycloalkyl, C₃-C₆cycloalkoxy, C₁-C₆ alkoxy, C₂-C₆ alkenyl, C₂-C₆ alkynyl, S(═O)_(n)(C₁-C₆alkyl), OSO₂(C₁-C₆ alkyl), OSO₂(C₁-C₆ haloalkyl), C(═O)NR_(x)R_(y),(C₁-C₆ alkyl)NR_(x)R_(y), C(═O)(C₁-C₆ alkyl), C(═O)O(C₁-C₆ alkyl),C(═O)(C₁-C₆ haloalkyl), C(═O)O(C₁-C₆ haloalkyl), C(═O)(C₃-C₆cycloalkyl), C(═O)O(C₃-C₆ cycloalkyl), C(═O)(C₂-C₆ alkenyl),C(═O)O(C₂-C₆ alkenyl), (C₁-C₆ alkyl)O(C₁-C₆ alkyl), (C₁-C₆ alkyl)S(C₁-C₆alkyl), C(═O)(C₁-C₆ alkyl)C(═O)O(C₁-C₆ alkyl), Het, phenyl, and phenoxy,wherein each alkyl, cycloalkyl, cycloalkoxy, alkoxy, alkenyl, alkynyl,Het, phenyl, and phenoxy are optionally substituted with one or moresubstituents independently selected from OH, F, Cl, Br, I, CN, NO₂, oxo,C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₁-C₆ hydroxyalkyl, C₃-C₆ cycloalkyl,C₃-C₆ halocycloalkyl, C₃-C₆ hydroxycycloalkyl, C₃-C₆ cycloalkoxy, C₃-C₆halocycloalkoxy, C₃-C₆ hydroxycycloalkoxy, C₁-C₆ alkoxy, C₁-C₆haloalkoxy, C₂-C₆ alkenyl, C₂-C₆ alkynyl, S(═O)_(n)(C₁-C₆ alkyl),S(═O)_(n)(C₁-C₆ haloalkyl), OSO₂(C₁-C₆ alkyl), OSO₂(C₁-C₆ haloalkyl),C(═O)NR_(x)R_(y), (C₁-C₆ alkyl)NR_(x)R_(y), C(═O)(C₁-C₆ alkyl),C(═O)O(C₁-C₆ alkyl), C(═O)(C₁-C₆ haloalkyl), C(═O)O(C₁-C₆ haloalkyl),C(═O)(C₃-C₆ cycloalkyl), C(═O)O(C₃-C₆ cycloalkyl), C(═O)(C₂-C₆ alkenyl),C(═O)O(C₂-C₆ alkenyl), (C₁-C₆ alkyl)O(C₁-C₆ alkyl), (C₁-C₆ alkyl)S(C₁-C₆alkyl), C(═O)(C₁-C₆ alkyl)C(═O)O(C₁-C₆ alkyl), NR_(x)R_(y), phenyl, andphenoxy; (j) X1 is S; (k) n=0, 1, or 2 (each independently); and (l)R_(x) and R_(y) are independently selected from H, C₁-C₆ alkyl, C₁-C₆haloalkyl, C₁-C₆ hydroxyalkyl, C₃-C₆ cycloalkyl, C₃-C₆ halocycloalkyl,C₃-C₆ hydroxycycloalkyl, C₂-C₆ alkenyl, C₂-C₆ alkynyl, S(═O)_(n)(C₁-C₆alkyl), S(═O)_(n)(C₁-C₆ haloalkyl), OSO₂(C₁-C₆ alkyl), OSO₂(C₁-C₆haloalkyl), C(═O)H, C(═O)(C₁-C₆ alkyl), C(═O)O(C₁-C₆ alkyl), C(═O)(C₁-C₆haloalkyl), C(═O)O(C₁-C₆ haloalkyl), C(═O)(C₃-C₆ cycloalkyl),C(═O)O(C₃-C₆ cycloalkyl), C(═O)(C₂-C₆ alkenyl), C(═O)O(C₂-C₆ alkenyl),(C₁-C₆ alkyl)O(C₁-C₆ alkyl), (C₁-C₆ alkyl)S(C₁-C₆ alkyl), C(═O)(C₁-C₆alkyl)C(═O)O(C₁-C₆ alkyl), and phenyl.
 2. A pesticidal compositionaccording to claim 1 wherein in said molecule said Ar₁ is a substitutedphenyl wherein said substituted phenyl has one or more substituentsindependently selected from the group consisting of C₁-C₆ haloalkoxy. 3.A pesticidal composition according to claim 1 wherein in said moleculesaid Ar₂ is a phenyl.
 4. A pesticidal composition according to claim 1wherein in said molecule said R3 is H.
 5. A pesticidal compositionaccording to claim 1 wherein in said molecule said R4 is H.
 6. Apesticidal composition according to claim 1 wherein in said moleculesaid R4 is a phenyl optionally substituted with one or more substituentsindependently selected from the group consisting of C₁-C₆ alkyl.
 7. Apesticidal composition according to claim 1 wherein in said moleculesaid R5 is phenyl wherein said phenyl is optionally substituted with oneor more substituents independently selected from the group consisting ofF, Cl, C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₁-C₆ alkoxy, or phenyl.
 8. Apesticidal composition according to claim 1 comprising a pesticidallyacceptable acid addition salt, a salt derivative, a solvate, or an esterderivative, of a said molecule.
 9. A pesticidal composition according toclaim 1 wherein said molecule has at least one H that is ²H or at leastone C is ¹⁴C.
 10. A pesticidal composition according to claim 1comprising at least one other compound selected from the InsecticideGroup, Acaricide Group, Nematicide Group, Fungicide Group, HerbicideGroup, AI Group, or Synergist Group.
 11. A pesticidal compositionaccording to claim 1 comprising a molecule according to claim 1 and aseed.
 12. A pesticidal composition according to claim 11 wherein saidseed has been genetically modified to express one or more specializedtraits.
 13. A pesticidal composition according to claim 1 wherein saidmolecule has one of the following structures


14. A pesticidal composition according to claim 13 and one or morecompounds selected from the insecticide group, acaricide group,nematicide group, fungicide group, herbicide group, AI group, orsynergist group.
 15. A pesticidal composition comprising a moleculeaccording to claim 13 and one molecule that has a mode of actionselected from the group consisting of acetylcholinesterase inhibitor,sodium channel modulator, chitin biosynthesis inhibitor, GABA-gatedchloride channel antagonist, GABA and glutamate-gated chloride channelagonist, acetylcholine receptor agonist, MET I inhibitor, Mg-stimulatedATPase inhibitor, nicotinic acetylcholine receptor, Midgut membranedisrupter, oxidative phosphorylation disrupter, and ryanodine receptor(RyRs).
 16. A pesticidal process comprising applying a pesticidalcomposition comprising a molecule according to claim 1 to an area tocontrol a pest, in an amount sufficient to control such pest.
 17. Apesticidal process according to claim 16 wherein said pest is selectedfrom the group consisting of beet army worm, corn ear worm, or greenpeach aphid.
 18. A pesticidal process comprising applying a pesticidalcomposition according to claim 1 to a genetically modified plant thathas been modified to express one or more specialized traits.
 19. Apesticidal process comprising: orally administering; or topicallyapplying; a pesticidal composition according to claim 1 to a non-humananimal to control endoparasites, ectoparasites or both.